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GROUP 13 ORGANOMETALLIC CHEMISTRY:
STERICALLY DEMANDING LIGANDS, METAL-METAL BONDING, AND
METALLOAROMATICY
by
BRANDON QUILLIAN
(Under the Direction of Gregory H. Robinson)
ABSTRACT
The syntheses and molecular structures of several organometallic group 13 compounds
and complexes are presented herein. The organometallic chemistry of RLi (R = 2,6-(4-t-
BuC6H4)2C6H3-) and R´Li (R´ = 2,6-(4-Me-C6H4)2C6H3-) was examined on group 13 halides to
yield a number of new compounds 1-8: RGaCl2(OEt2) (1), R2GaCl (2), RAlBr2(OEt2) (3),
[RAlCl(OEt2)]2O (4), R3In (5), [R GaCl3][Li(OEt2)2] (6), [R InCl3][Li(OEt2)(THF)] (7), R 3In.
Compounds 5 and 8 are notable as the first tris-m-terphenyl-group 13 compounds, while 4 is an
interesting oxo-bridged-di(m-terphenyl-aluminum chloride) complex with exceptionally long
Al Cl bonds. Sodium metal reduction of 1 provides a rare catenated tri-gallium complex,
[R3Ga3][Na(OEt2)]3 (9).
Additionally, the organometallic chemistry at the group 13 group 4 interface was
explored, wherein three new compounds were isolated: Cp2Hf(ER)2 (10, E = Ga; 11, E = In; R =
2,6-(2,4,6-i-Pr3C6H2)2C6H3-) and (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (R = 2,6-(4-t-
BuC6H4)2C6H3-) (12). Compounds 10 and 11 contain the first reported group 13 Hf bonds, while
compound 12 is the only compound with gallium engaged in bonding with two zirconium atoms.
Extending the organometallic chemistry of m-terphenyl ligands to the group 4
metallocenes gave the first m-terphenyl titanium(III) radical Cp2TiR´ (13) and the first m-
terphenyl zirconocene(IV) compound, Cp2ZrR(Cl) (14) (R = 2,6-(4-t-BuC6H4)2C6H3-).
This research project also involved the study of heterometallic aromaticity, which
ultimately produced the first gallepin, bis(gallepin)2·TMEDA (18), by the reaction of 2,2 -
dilithio-Z-stilbene(TMEDA)2 (16) and GaCl3. The aromatic nature of the gallepin was evaluated
using Nucleus-Independent Chemical Shifts (NICS) and compared to that of borepins.
Additionally, the -donor properties of N-heterocyclic carbenes were evaluated on
mesityl-group 13 dihalides, wherein several new carbene-mesityl-group 13 dihalide adducts were
prepared: MesGaCl2(:L) (19), MesAlBr2(:L) (20), MesInBr2(:L) (21) (Mes = 2,4,6-Me3C6H2-; :L
= :C 2). Potassium graphite reduction of 19 yielded a rare meso-digallane, [MesGaCl(:L)]2 (22),
with four-coordinate gallium atoms, while reduction with potassium metal unexpectedly
produced an unprecedented neutral Ga6-octahedron cluster, Mes4Ga6(:L)2 (23). NICS
calculations were used to support its aromatic properties and compared with that of the
thoroughly studied dianionic hexaborate octahedron, [B6H6]-2.
In conjunction with these studies a new detailed synthetic protocol to prepare
Arduengo’s carbene (26) from adamantylammonium chloride was established and full single
crystal X-ray structural analysis reported.
INDEX WORDS: alkali metal reduction, aluminum, aromaticity, computations,
cyclopentadienyl, gallepin, gallium, group 4, group 13, hafnium, indium,
main group metals, mesityl, metallocene, metalloaromaticity, metal metal
bonds, m-terphenyl, N-heterocyclic carbene, Nucleus-Independent
Chemical Shifts, organometallic, sterically demanding ligands, titanium,
zirconium
GROUP 13 ORGANOMETALLIC CHEMISTRY:
STERICALLY DEMANDING LIGANDS, METAL-METAL BONDING, AND
METALLOAROMATICY
by
BRANDON QUILLIAN
B.S., Armstrong Atlantic State University, 2003
A Dissertation Submitted to the Graduate Faculty of The University of Georgia in Partial
Fulfillment of the Requirements for the Degree
DOCTOR OF PHILOSOPHY
ATHENS, GEORGIA
2008
© 2008
Brandon Quillian
All Rights Reserved
GROUP 13 ORGANOMETALLIC CHEMISTRY:
STERICALLY DEMANDING LIGANDS, METAL-METAL BONDING, AND
METALLOAROMATICY
by
BRANDON QUILLIAN
Major Professor: Gregory H. Robinson
Committee: George F. Majetich Robert S. Phillips
Electronic Version Approved: Maureen Grasso Dean of the Graduate School The University of Georgia December 2008
iv
DEDICATION
I dedicate this dissertation to my wife, Jennifer Quillian, whose loyalty and sacrifice gave
me the strength to carry on in my desperate moments, and to my daughter, Kyleigh, whose smile
and laughter consoled me. To those who were not able to witness my greatest accomplishment,
my mother and father, Rosa Mae Rucker and Charles Edward Quillian, who gave me this
precious life but left this world long before I ever knew them. To my Aunt Fannie whom raised
me in my parents’ stead.
v
ACKNOWLEDGEMENTS
I owe great gratitude to my wife whose perseverance and patience never waned. It is with
her support and understanding that I am able to complete The University of Georgia doctoral
program in chemistry. Special thanks goes out to my committee members, Dr. George Majetich
and Dr. Robert S. Phillips, for your guidance and support. I would also like to thank Dr.
Yuzhong Wang. His ingenuity, knowledge, and guidance were invaluable assets. Last but not
least, I would also like to thank Dr. Gregory H. Robinson for giving me the opportunity to
become a better scientist and motivation and support throughout my years at UGA.
vi
TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS.........................................................................................................v
LIST OF TABLES.................................................................................................................. viii
LIST OF FIGURES ....................................................................................................................x
CHAPTER
1 INTRODUCTION .....................................................................................................1
1.1 Purpose of Study..............................................................................................1
1.2 Organometallic Chemistry History and Origins................................................2
1.3 General Organometallic Synthetic Techniques.................................................5
1.4 Chemistry and Properties of the Group I, II, 13 Elements.................................6
1.5 Sterically Demanding m-Terphenyl Ligands ..................................................19
1.6 Main Group Metal Metal Multiple Bonding..................................................22
1.7 Metalloaromaticity.........................................................................................33
2 RESULTS AND DISCUSSIONS ............................................................................39
2.1 Less-sterically Demanding m-Terphenyl Group 13 Complexes.....................39
2.2 Organometallic Group 13 Group 4 Complexes .............................................68
2.3 m-Terphenyl Group 4 Metallocenes ...............................................................81
2.4 Gallepins .......................................................................................................89
2.5 Examinations of Carbenes in Group 13 Chemistry.......................................104
2.6 A New Synthetic Procedure for Arduengo’s Carbene...................................126
vii
3 Conclusion.............................................................................................................133
3.1 Concluding Remarks....................................................................................133
4 EXPERIMENTAL.................................................................................................137
4.1 General Background ....................................................................................137
4.2 Preparation and Characterization of Starting Materials.................................139
4.3 Syntheses of m-Terphenyl Group 13 Complexes........................................ .143
4.4 Syntheses of Organometallic Group 13 Group 4 Complexes .......................147
4.5 Syntheses of m-Terphenyl Group 4 Metallocenes.........................................148
4.6 Syntheses of Gallepins and Precursor...........................................................149
4.7 Syntheses of Carbene Group 13 complexes.................................................151
4.8 Synthesis of Arduengo’s Carbene ................................................................153
REFERENCES .......................................................................................................................155
APPENDICES
A CRYSTALLOGRAPHIC DATA...........................................................................172
B RESEARCH PUBLICATIONS .............................................................................284
viii
LIST OF TABLES
Page
Table 2.1: Selected bond distances [Å] and angles [°] for RGaCl2(OEt2) (1)..............................45
Table 2.2: Selected bond distances [Å] and angles [°] for R2GaCl (2)........................................46
Table 2.3: Selected bond distances [Å] and angles [°] for RAlBr2(OEt2) (3) ..............................48
Table 2.4: Selected bond distances [Å] and angles [°] for [RAlCl(OEt2)]2O (4). ........................50
Table 2.5: Selected bond distances [Å] and angles [°] for R3In (5).............................................54
Table 2.6: Selected bond distances [Å] and angles [°] for [R GaCl3][Li(OEt2)2] (6)...................58
Table 2.7: Selected bond distances [Å] and angles [°] for [R InCl3][Li(OEt2)(THF)] (7)............61
Table 2.8: Selected bond distances [Å] and angles [°] for R 3In (8)............................................62
Table 2.9: Selected bond distances [Å] and angles [°] for [R3Ga3][Na(OEt2)]3 (9) .....................66
Table 2.10: Selected bond distances [Å] and angles [°] for Cp2Hf(GaR)2 (10) ...........................72
Table 2.11: Selected bond distances [Å] and angles [°] for Cp2Hf(InR)2 (11) ............................73
Table 2.12: Selected bond distances [Å] and angles [°] for (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR)
(12) ...........................................................................................................................77
Table 2.13: Selected bond distances [Å] and angles [°] for Cp2TiR (13) ....................................85
Table 2.14: Selected bond distances [Å] and angles [°] for Cp2Zr(R)(Cl) (14) ...........................88
Table 2.15: Selected bond distances [Å] and angles [°] for 2,2 -dilithio-Z-stilbene(TMEDA)2,
(16) ...........................................................................................................................95
Table 2.16: Selected bond distances [Å] and angles [°] for [spiro-[6,6]-bis-
stilbenylgallium][Li(OEt2)] (17) ...............................................................................97
ix
Table 2.17: Selected bond distances [Å] and angles [°] for bis(gallepin)2·TMEDA (18) ..........101
Table 2.18: NICS, NICS , and NICS zz for seven-membered rings in 18, 18Cl(NMe3), 18Cl,
Gallepin, and Borepin..............................................................................................103
Table 2.19: NICS, NICS , and NICS zz for phenyl rings in 18, 18Cl(NMe3), and 18Cl ...........104
Table 2.20: Selected bond distances [Å] and angles [°] for MesGaCl2(:L) (19) ........................112
Table 2.21: Selected bond distances [Å] and angles [°] for MesAlBr2(:L) (20).........................113
Table 2.22: Selected bond distances [Å] and angles [°] for [MesInBr2(:L)] (21) ......................115
Table 2.23: Selected bond distances [Å] and angles [°] for [MesGaCl(:L)]2 (22) .....................118
Table 2.24: Selected bond distances [Å] and angles [°] for Mes4Ga6(:L)2 (23).........................122
Table 2.25: Bond order for various bonds are calculated at the PW91PW91/6-31G*//B3LYP/6-
311+G** for Ga6Ph4(:L )2 (:L = :C(HNCH)2) (23a) ................................................125
Table 2.26: Selected bond distances [Å] and angles [°] for Arduengo’s carbene (AdL:) (26) ...130
x
LIST OF FIGURES
Page
Figure 1.1: Anion of Zeise’s Salt ................................................................................................3
Figure 1.2: Structure of Ferrocene ...............................................................................................5
Figure 1.3: Beryllium chain polymer with three-center two-electron bonds .................................7
Figure 1.4: Electron deficient three-center two-electron bonds of diborane, B2H6........................8
Figure 1.5: Schlenk equilibrium of Grignard reagent in solution................................................10
Figure 1.6: Structure of B12 icosahedral unit..............................................................................12
Figure 1.7: Octahedral AlF3 and AlCl3 dimer ............................................................................16
Figure 1.8: Structures of [Ph3Al]2 and (Mes)3Al ........................................................................19
Figure 1.9: Structures of common m-terphenyl ligands..............................................................20
Figure 1.10: Depiction of dissociation/dimerization in solution and solid and donor-acceptor
bonding model for R2Sn=SnR2 (R = -CH(SiMe3)2 .....................................................24
Figure 1.11: Molecular structure of tetrakis[bis(trimethylsilyl)methyl]dialane, R2Al AlR2 .......26
Figure 1.12: Bonding model for the heavier main group metallynes ..........................................27
Figure 1.13: Schematic depiction and single crystal X-ray structure of gallyne, Na2[RGa GaR]
2,6-(2,4,6-i-Pr3C6H2)2C6H3-). ............................................................................29
Figure 1.14: Structures of [Mg(Priso)]2 and [Mg(Nacnac)]2 .......................................................31
Figure 1.15: Structures of compounds containing group 12 metal metal bonds.........................32
Figure 1.16: Schematic depiction of CbFe(CO)3........................................................................34
xi
Figure 1.17: Single crystal X-ray structure of Na[GaR]3............................................................34
Figure 1.18: Orbital description of [H3Ga3]2- .............................................................................35
Figure1.19: Structure of K2[Ga4R2] ( R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-) .....................................36
Figure 1.20: Structure of Na2[Ga4R4](THF)2 (R = t-Bu3Si-).......................................................37
Figure 2.1: Structures of 2,6-(4-t-BuC6H4)2C6H3- (R) and 2,6-(4-Me-C6H4)2C6H3- (R´) ............40
Figure 2.2: Molecular structure of RGaCl2(OEt2) (1).................................................................45
Figure 2.3: Molecular structure of R2GaCl (2)...........................................................................46
Figure 2.4: Molecular structure of RAlBr2(OEt2) (3) .................................................................48
Figure 2.5: Molecular structure of [RAlCl(OEt2)]2O (4) ............................................................50
Figure 2.6 Table for torsion angles (deg) and Newman projection of 4: “looking down the
Al O Al vector”.......................................................................................................51
Figure 2.7: “No bond/double bond” resonance model for -halomethyl ethers ..........................52
Figure 2.8: The “no-bond/double-bond” resonance model for 4.................................................53
Figure 2.9: Molecular structure of R3In (5)................................................................................54
Figure 2.10: Molecular structure of [R GaCl3][Li(OEt2)2] (6) ....................................................58
Figure 2.11: Molecular structure of [R InCl3][Li(OEt2)(THF)] (7) .............................................61
Figure 2.12: Molecular structure of R 3In (8) .............................................................................62
Figure 2.13: Space filling model of R 3In (8) .............................................................................63
Figure 2.14: Molecular structure of [R3Ga3][Na3(OEt)3] (9).......................................................66
Figure 2.15: Molecular structure of Cp2Hf(GaR)2 (10) ..............................................................72
Figure 2.16: Molecular structure of Cp2Hf(InR)2 (11)................................................................73
Figure 2.17: DFT level calculated HOMO, HOMO-1 and HOM-2 orbitals for Cp2M(ER)2
compounds................................................................................................................74
xii
Figure 2.18: Molecular structure of (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12) .........................77
Figure 2.19: PW91PW91/LANL2DZ optimized structure of (C10H8)(CpZr)2(μ-H)(μ-Cl)(μ-GaR)
(R = 2,6-Me2C6H3) (12a)...........................................................................................78
Figure 2.20: ChemDraw representation of 12 depicting with bridging and localized chloride and
hydride ligands..........................................................................................................79
Figure 2.21: Space filling model of (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12) .........................80
Figure 2.22: Molecular structure of Cp2TiR (13).......................................................................85
Figure 2.23: Molecular structure of Cp2Zr(R)(Cl) (14) ..............................................................88
Figure 2.24: Tropylium ion localized cation and delocalized cation, borepin, and gallepin ........90
Figure 2.25: Molecular structure of 2,2 -dibromo-Z-stilbene (15) ..............................................92
Figure 2.26: Molecular structure of 2,2 -dilithio-Z-stilbene(TMEDA)2 (16)...............................95
Figure 2.27: Molecular structure of [spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)] (17) ...............97
Figure 2.28: Molecular structure of bis(gallepin)2·TMEDA, (18).............................................100
Figure 2.29: B3LYP/LANL2DZ optimized geometries of 18Cl(NMe3) and 18Cl ...................102
Figure 2.30: General carbene shown as singlet state and Arduengo’s carbene..........................104
Figure 2.31: General N-heterocyclic carbene depicting electron with drawing effects of the -
nitrogen and -donation into the empty p-orbital of carbenic carbon........................105
Figure 2.32: Molecular structure of MesGaCl2(:L) (19) ...........................................................112
Figure 2.33: Molecular structure of MesAlBr2(:L) (20)............................................................113
Figure 2.34: Molecular structure of MesInBr2(:L) (21) ...........................................................115
Figure 2.35: A view of the unit cell of [MesInBr2(:L)][InBr3(:L)] (21)....................................116
Figure 2.36: Molecular structure of [MesGaCl(:L)]2 (22) ........................................................118
Figure 2.37: Molecular structure of Mes4Ga6(:L)2 (23) ............................................................122
xiii
Figure 2.38: The B3LYP/6-311+G** optimized geometry of Ga6Ph4(:L )2 (:L = :C(HNCH)2)
(23a) .......................................................................................................................125
Figure 2.39: Molecular structure of glyoxal-bis-(1-adamantyl)imine (24)................................128
Figure 2.40: Molecular structure of Arduengo’s carbene (AdL:) (26) ......................................130
Figure 2.41: A view of the unit cell of Arduengo’s carbene (AdL:) (26) ..................................131
1
CHAPTER 1
INTRODUCTION
1.1 Purpose of Study
All of chemistry is centered around the chemical bond. Probably the least well-studied
bonding scenario, however, is the metal metal bond. In fact metal metal bonding was once
considered impossible curiosities. The organometallic community has embraced this challenge
and has put forth a large number of reports that has expanded the scope and knowledge of our
understanding of such bonding. Regarding main group metal metal bonding, these investigations
were not seriously embarked upon until fairly recently. Hence, this field of organometallic
chemistry remains relatively underdeveloped. We continue in this quest to obtain organometallic
compounds containing main group metal metal bonds so as to provide new insights into the
fundamental principles of structure and bonding.
Another aspect of this research project focuses on aromaticity. This theory, once reserved
for carbon, has transcended its founding principles and no more is the prerequisites of 4n+2 -
electrons and a planar cyclic structure mandatory. Indeed, aromaticity is far more intricate than
previously suggested and has been observed in three-dimensions, 4n -electron systems, and
metallic species. The latter of these has been a concentrate in organometallic chemistry. In
particular, reports of compounds containing all metallic aromatic rings (metalloaromatic) have
rejuvenated the discussion of aromaticity. Although some exquisite examples of organometallic
compounds exhibiting metalloaromaticity have been published, this genre of chemistry is still
2
severely underdeveloped. Hence, an alternative purpose of this study was to prepare
organometallic compounds that exhibit metalloaromaticity and heterometallic aromaticity (cyclic
compounds with at least one metallic atom that display aromatic properties).
1.2 Organometallic Chemistry History and Origins
Organometallic chemistry is the combination of two disparate chemical
disciplines traditional organic chemistry and inorganic chemistry. Surprisingly, organometallic
chemistry is a relatively quiescent topic in both organic and inorganic textbooks, being
mentioned with a fleeting paragraph. This is appalling due to the ubiquitous nature of
organometallic compounds in both disciplines.
Compounds possessing at least one direct carbon metal bond are considered
organometallic. The ubiquitous Grignard reagents are quintessential examples. Because
metalloids (B, Si, Ge, P, As, Se, Te) are not strictly metallic, categorizing compounds with
carbon metalloid bonds as either organometallic or organic may seem ambiguous. This dilemma
may be elegantly resolved by J. S. Thayer’s interpretation, which proposed that a compound
containing a metalloid less electronegative than carbon may be considered organometallic.1
The origins of organometallic chemistry can be traced back to an organoarsenic
compound prepared by Cadet de Gassicourt in 1760 known as “Cadet’s fuming arsenical liquid”,
which was later identified as (CH3)4As2 by Robert Bunsen (1837-1843).1 These accounts have
been summarized in a recent essay.2 In 1827 W. C. Zeise reported another organometallic
complex, K[C2H4PtCl3]•H2O (Zeise’s salt), which is considered by most to be the first
organometallic compound (arsenic is considered a metalloid). The structure and bonding of
Zeise’s salt was steeped in controversy and would not be resolved until its single crystal X-ray
3
structure was reported 85 years later,3 which revealed an ethylene molecule -bound to a Pt atom
in a side-on fashion (Figure 1.1).4 Zeise’s salt is notable as the first report of an organic molecule
bonded to a metal through -electrons and brought about the concept of hapticity.5
Pt
Cl
ClCl
H
H
H
H
-
Figure 1.1. Anion of Zeise’s Salt
The focus of organometallic chemistry began to shift to the main group elements with the
isolation of the first organozinc compound, diethylzinc ((C2H5)2Zn), by Edward Frankland6 in
1849 (Though zinc, a group 12 element, formally resides in the d-block section of the periodic
table, its chemistry is more similar to that of the group II elements. With a filled d-orbital (d10s2
electronic configuration), the two s-electrons dominate its chemistry. In fact, zinc behaves more
like beryllium than any of the transition metals). Not only were organozinc compounds notable
as the first organo-main group compounds but they were also the first to have appreciable
synthetic utility. The zenith of organozinc chemistry did not last for long because in 1900 Victor
Grignard discovered organomagnesium compounds, which quickly replaced organozinc
compounds in synthetic protocols due to facile preparation, ease of handling, and reaction
efficacy.
During the period of 1900-1950, there was a lull in the development of organometallic
chemistry until a seemingly accidental discovery sparked the birth of modern-day organometallic
4
chemistry. In 1951 Kealy and Pauson attempted to synthesize fulvalene (H4C5=C5H4) by reaction
of cyclopentadienyl magnesium bromide, CpMgBr (Cp = C5H5) with anhydrous iron(III)
chloride (Eq.1.1). However, the reaction did not produce the desired fulvalene, but instead gave
an orange air-stable compound with a molecular formula of C10H10Fe.7 It is noteworthy that in
1952 Miller and co-workers independently synthesized the identical compound by reaction of
cyclopentadiene with metallic iron in the presence of metal oxides (Eq. 1.2).8
MgBr
fulvaleneX
(C5H5)2Fe + 1/2C10H10 + 3 MgBrCl
+ FeCl33
+ FeMetal oxide
(C5H5)2Fe + H22
The structural assignment of C10H10Fe was quite a quandary as spectroscopic data did
correlate with the initial assessment, wherein it was thought that two Cp ligands were -bound to
an iron center. In 1952, two groups, Wilkinson et al.9 and Fischer et al.10,11, independently
postulated that the Cp ligands were bound to the iron atom in a novel -fashion, wherein the
cyclic array of p-orbitals on the Cp ligands overlapped the d-orbitals of the metal to form a
“sandwiched” iron complex. This “sandwich” description was confirmed by spectroscopic
evidence, i.e. only one C H stretch in the infrared spectrum, diamagnetism, and an effectively
zero dipole moment. Its structure was unambiguously characterized by single crystal X-ray
(1.1)
(1.2)
5
crystallographic analysis in 1956 and confirmed its structure.12 This renowned compound is of
course ferrocene (Figure 1.2). It is interesting to note that the term “ferrocene” replaced the
formal name of dicyclopentadienyliron because Friedel-Crafts acylations of this compound were
readily achieved. This line of reasoning mimicked the vernacular of benzene, wherein “ene”
evokes aromaticity.
Organometallic chemistry has blossomed into a flourishing division of chemistry today
that has its own set of journals, books, and monograms. It is an interdisciplinary study that is
encountered in organic, inorganic, computational, physical, and biological chemistries. The
storied history of organometallic chemistry is quite unique with its periods of inactivity and
moments of eureka, however today it is well established. It is safe to say that new insights into
organometallic chemistry will be revealed in the impending future.
Fe
Figure 1.2. Structure of Ferrocene
1.3 General Organometallic Synthetic Techniques
Organometallic chemistry is not much different from other synthetic chemical
disciplines. The major difference is dealing with air- and moisture-sensitive materials, which
require some special techniques. In general, however, organometallic compounds are prepared
by three common methods: 1) reaction of metal or metal derivative with an organic reagent, 2)
oxidations/reductions, and 3) metathesis reactions of nucleophilic organic reagents with metal
halides.
6
Due the inherent instability of metal carbon bonds, organometallic species readily
hydrolyze, thus special synthetic measures known as Schlenk techniques13 have been developed
to strictly exclude air and moisture. Bench-top reactions are performed on a double manifold
system (Schlenk line) equipped with purified nitrogen or argon gas and vacuum pump. Glassware
is cleaned with great scrutiny and stored and dried in a 180°C oven, while solvents are rigorously
dried, freshly distilled, and degassed prior to use. Because glassware is stored in air, all reaction
vessels are repeatedly purged and flushed with argon. To avoid exposure to air, dripping funnels,
syringes, or a long flexible tubes known as cannulas are commonly used to transfer reagents.
In conjunction with Schlenk line techniques a dry box is commonly utilized to weigh
reactants, conduct experiments that require solid reagent transfer, store air- and moisture-
sensitive reagents, and prepare samples for characterization.
The most practical means to unambiguously characterized organometallic compounds is
by single crystal X-ray crystallographic analysis, however, 1H- 13C-nuclear magnetic resonance
spectroscopy (NMR), infrared spectroscopy (IR), ultraviolet-visible spectroscopy (UV-vis),
electron spin resonance spectroscopy (ESR), elemental analysis (EA), and mass spectrometry
(MS) can be indispensable aids. All characterization techniques require that the sample be
prepared expeditiously in sealed sampling vessels to avoid decomposition.
1.4 Chemistry and Properties of the Group I, II, 13 Elements
The group I, II, and 13 elements were routinely employed in this research project. The
purpose of this section is to provide some background on the fundamental properties of these
elements and insights into their chemistry.
7
Group 13 organometallic chemistry would be difficult to pursue without utilizing its
lower valent neighbors the group I and II elements. These elements not only provide a method
to form carbon metal bonds, by which the very nomenclature of organometallic is derived, but
they also provide excellent reducing agents. All of the group I and II elements are metals (alkali
metals and alkaline earth metals, respectively) and primarily form ionic complexes. However,
beryllium, the smallest of the group II elements, is somewhat of an anomaly. Large charge
density resides about beryllium and contributes significantly to its peculiar behavior. For
example, beryllium chemistry is dominated by covalent bonds and has a common coordination
number of four, whereas magnesium and calcium are commonly hexa-coordinate, and strontium
and barium can even eclipse this high-coordination number. Moreover, beryllium compounds
routinely form polymeric electron-deficient bonds (Figure 1.3) termed “three-centered two-
electron bonds” (3c-2e bonds).
Be Be Be
R
R
R
R
R
R
R = Halide or -CH3
Be
Figure 1.3. Beryllium chain polymer showing three-center two-electron bonds
Lipscomb rationalized 3c-2e bonds in his seminal studies of borohydrides.14,15 Diborane,
B2H6, is a quintessential example. It consists of four terminal B H bonds and two bridging 3c-2e
B H B bonds, which have adequate orbital overlap between the two boron sp3-hybridized
orbitals and spherical bridging hydrogen s-orbitals (Fig. 1.4). The terminal B H bond distances
8
(1.192 Å) are considerably shorter than the bridging B H B bonds (1.329 Å), evidence that the
terminal covalent bonds are much stronger.16 This bonding scenario has also been observed in
metallic clusters, organometallic species, and metal halides.17-19
BH
H
BH
H
H
H
sp3-orbitals-orbital
Figure 1.4. Electron deficient three-center two-electron bonds of diborane, B2H6
The ability to form highly reactive carbon-metal bonds is perhaps the most remarkable
shared characteristic between the group I and II elements. In particular, organolithiums or
organomagnesiums are routinely used to synthesize organo-group 13 halides (RmEXn, R = alkyl,
aryl, E = B Tl, X = halide, m = 1-3, n = 3 - m) via metathesis reactions with group 13 salts, EX3
(Eq. 1.3), which serve as intermediates for more intricate chemistry.
RLi + EX3 REX2 + LiX
RMgX + EX3 REX2 + MgX2
Organolithium compounds, RLi, may be prepared by reaction of two equivalents of
lithium metal with an organic halide (RX) (Eq. 1.4), by deprotonation of organic residues with
highly reactive alkyllithium compounds such as n-butyllithium (n-BuLi) (Eq. 1.5), or by metal-
halogen exchange reaction between organic halides (R X) (Eq. 1.6).
(1.3)
9
RX + 2Li RLi + LiX (1.4)
RLi + R'H RH + R'Li (1.5)
RLi + R'X RX + R'Li (1.6)
RX + Mg RMgX (1.7)
Organomagnesium halides (Grignard reagents), RMgX, are prepared by reaction of
magnesium metal with an organic halide, wherein magnesium metal oxidatively inserts into the
C X bond (Eq. 1.7). Of special note, a thin layer of magnesium oxide must be removed from the
metal in order to initiate the reaction by a process known as “activation”. Sonication, agitation,
and/or catalyst (1,2-dibromoethane) are several techniques used to activate magnesium metal.
Once the metal is activated, the reaction is generally highly exothermic as long as air and
moisture is excluded at all times.
Organomagnesium compounds are frequently written as RMgX, and for most purposes
this representation is suffice, however in solution a complex equilibrium (Schlenk equilibrium) is
a more accurate depiction (Figure 1.5).20
10
RX + Mg
RMgXRMg
X
X
MgR R2Mg + MgX2XMg
X
R
MgR
Mg
X
X
MgR2RMg+ + RMgX2
-
Figure 1.5 Equilibrium of Grignard reagent in solution
Organolithiums are more reactive than their magnesium counterparts, yet they are easily
handled and tend to avoid side reactions such as non-specific C H activation, which is often
observed for Grignard reagents. Many organomagnesium and organolithium reagents are
commercially available, and if stored properly, they are stable for months. The choice to use
either organolithium or magnesium reagents depends on ease of preparation, commercial
availability, specific reaction conditions, and substrates involved.
Alkali or alkaline earth metal reductions of organo-group 13 halides have been
established as an effective strategy to obtain compounds with metal metal bonds. A detailed
discussion of this chemistry is provided in the proceeding chapters. Due to more robust reactivity
and lower reduction potentials, alkali metal reductions are cited more often than their alkaline
earth metal counterparts in these procedures because the third ionization energies of the group 13
elements are very large (2704-3659 kJ/mol). The group I metals (alkali metals) more readily
donate their electron and as the column descends relative reactivity increases due to poorer
internal shielding of the d-orbitals; hence rubidium and cesium are extremely reactive metals.
Counterintuitively, lithium is the least reactive but has the lowest reduction potential of the group
11
(Caution: group I metals are highly sensitive to water and moisture, and in some instances even
explosive, thus great care should always be practiced when handling them).
A commonly employed reducing agent in organometallic synthetic procedures is
potassium graphite (KC8), which is part of a larger class of molecules called inclusion
compounds or “lamellar” compounds. Potassium graphite may be conveniently prepared by
melting potassium metal with graphite (Eq. 1.8), wherein the potassium metal readily inserts into
the well-separated (3.35 Å) sheets of graphite.
K + 8 C(graphite) KC8 (1.8)
In some instances, reductions of organometallic halides with potassium graphite have
shown able to elicit group 13 metal-metal bonding, where the otherwise sodium or potassium
metal reductions could not (vide infra). This is primarily because metal metal bonds are
kinetically stabilized, thus the reduction rate of the organometallic substrate is vitally important.
Because these reductions are heterogeneous, the large surface area of potassium graphite allows
for excellent interaction with the solubilized organometallic substrate. On the other hand, sodium
or potassium metal is usually divided by hand into tiny pieces and is extremely difficult to
approach the size of potassium graphite. Of course, this lowers the rate of reduction because of
less interaction between metal and the solubilized substrate.
It has been demonstrated that the metal reductant may also influence the structure and
bonding of complexes containing group 13 metal metal bonds. For example, reduction of
RGaCl2 (R 2,6-(2,4,6-i-Pr3C6H2)2C6H3-) with sodium metal provides a gallium gallium triple
bond (digallyne) Na2[RGa GaR however when potassium metal is employed a tetragallium
12
dianion, K2[Ga4R2],22 with a planar cyclic Ga4 metallic core is formed (vide infra). The size of
the alkali metal reductant was cited as critical to the different formations, as they interact
strongly with the group 13 elements. Interestingly, computations have proposed that lithium can
interact with gallium more strongly than either sodium or potassium.23 In some instances,
however, differences in reducing metal provide essentially identical final products. This is
observed when RGaCl2 (R = 2,6-Mes2C6H3, Mes =2,4,6-Me3C6H2-) is reduced with either
sodium or potassium, which forms isoelectronic cyclotrigallenes, M2[GaR]3 (M = Na,24 K,25 Mes
= 2,4,6-Me3C6H2-), regardless of which metal is used.
1.4.2 The Group 13 Elements
With exception of boron, a metalloid, the group 13 elements are metals. Boron, the
lightest of the group 13 elements, is a black solid with a metallic luster and consisting of a
number of allotropes. Most notable is the naturally occurring B12-icosahedron (Fig.1.6). Boron is
very distinct from the rest of the group 13 elements being more similar to silicon. This disparate
nature of boron from its group 13 members and close similarity to silicon is demonstrated by
comparing their electronegativity values (Pauling electronegativity; B = 2.040, Si = 1.900; Al =
1.61, Ga = 1.81, In = 1.78,), atomic radii (B = 0.85 Å Si = 1.10 Å; Al = 1.25, Ga, 1.30, In, 1.81),
and the fact that both boron and silicon have semiconductor properties.
= B
Figure 1.6. Structure of B12 icosahedral unit
13
Aluminum, the second lightest group 13 element, is a strong, silvery-white metal that is
prized for its light weight. Though aluminum is quite plentiful, it was once arduously difficult to
extract from its ubiquitous ores and once more treasured than gold. Today aluminum is produced
on an industrial scale by the Hall-Héroult process,26 whereby alumina is dissolved in molten
cryolite and subjected to electrolysis. A pound of aluminum today cost about a dollar, whereas
gold is now traded at $800/oz.
Gallium is a silvery, low-melting metal (30°C) that expands on solidification. Similar to
mercury, it is a liquid just above room temperature and commonly used in high-temperature
thermometers, however, gallium is not as toxic as mercury. Interestingly, the trend of increasing
atomic radius with column descent is at odds when transitioning from Al (1.48 Å) to Ga (1.26
Å).
Indium and thallium are also low meting metals, though not to the extent of gallium, and
are easily malleable. Interestingly, indium is slightly radioactive, decaying with -emission,
however its half-life is more that 400 trillion years, thus it is relatively safe to handle. Thallium,
on the other hand, is a highly toxic element that was commonly used in rat poisons. This practice
has been discontinued in the United States.
The chemistry of the group 13 elements varies from element to element, principally due
to internal electronic configurations. For instance, boron and aluminum contains only s and p
orbitals, while indium, gallium, and thallium contains a full compliment of d10 electrons.
Thallium also includes a filled f14 orbital, which contributes significantly to its anomalous
chemistry. There are, however, prevailing common characteristic between these elements. With
three valance electrons, the +3 oxidation state is favored for this group. Lower oxidation states
(+1 and +2) can also be obtained at very low temperatures but have a propensity to
14
disproportionate to metal and the +3 oxidation state with increasing temperature (Eq. 1.9).
Utilizing sterically demanding ligands has been an effective method to stabilize low-valent group
13 organometallic compounds (vide infra). Of the lower oxidation states, the +1 oxidation state
is more often observed, being somewhat common for In and readily obtained for Tl. In fact, Tl+3
is oxidizing due in part to the “inert pair” effect, which occurs when a pair of electrons in the low
energy s-orbital becomes difficult to ionize. This effect is more prevalent for the heavier p-block
main group elements (Sn, Pb, Sb, Bi, Te).
3 MX MX3 + M
(1.9)
Perhaps the most dominant feature of group 13 chemistry is the highly Lewis acidic
nature of the elements. Because trivalent group 13 species are commonly sp2-hybridized with
trigonal planar geometry, the unoccupied p-orbital makes them powerful Lewis acids that readily
accepts electron density from Lewis bases to obtain closed shelled, four-coordinate, Lewis
acid/base adducts, R3M LB. Coordination numbers of three and four are common for the group
13 elements, however higher-orders can be obtained, especially for the heavier members with d-
shell (Ga, In, Tl) valances.
1.4.3 The Group 13 Halides
The group 13 metal(III) halides, MX3, are important starting materials for the synthesis of
organo-group 13 halides, RMX2 or R2MX, which frequently serve as intermediates in a number
of synthetic protocols. All of the group 13 trihalides, MX3, are known except for TlI3, and their
geometries vary with element, halide, and physical state. All boron halides, BX3, are trivalent
15
monomers, due to effective overlap of the non-bonding electrons on the halides with the empty
p-orbital of boron. As a consequence, the acidity of the boron atom gradually increases as orbital
overlap lessens. Thus, BF3 is less acidic than BI3. Conversely, an opposite trend is observed for
the heavier EX3 (E = Al, Ga, In, Tl, X = halide) members, which preclude n p -bonding,
wherein Lewis acidity drops off as the electronegativity of the halide diminishes. Interestingly,
aluminum(III) fluoride (AlF3) and aluminum(III) chloride (AlCl3) (Fig.1.7) have polymeric
octahedral structures (AX6) with infinite lattices in the solid state, however in the liquid or gas
states aluminum chloride exist as a dimer, Al2Cl6, with two Al Cl Al bridges (Fig. 1.7). AlBr3
and AlI3 share this dimeric nature in all states. Surprisingly, although gallium is only one period
below aluminum, its halides are monomers (GaX3), similar to those of boron. Indium(III)
halides, InX3 (X = F, Cl, Br), are more similar in structure to AlCl3, but the structure of InI3 is
unknown. As alluded to earlier, Tl is considerably different from the metallic group 13 members
and this is reflected in its halides, as Tl(III) halides, TlX3 (X = Cl, Br), are fairly unstable and
readily disproportionate to a mixture salts Tl(TlCl4), Tl(TlX6),Tl2Cl3. TlF3 is known to have a 9-
coordinate tricapped trigonal prismatic structure.
The group 13 metal monohalides, MX, are also useful regents in synthetic protocols. In
particular, Linti27 and Schnöckel28 have employed putative in situ generated “GaI” and “AlI” to
synthesize a number of high-order group 13 clusters. The group 13 monohalides are known for
all of the metals, however TlX is by far more stable. Both InX and TlX are commercially
available.
16
Al
F
F F
F
F
F
Al
Cl
Cl
Al
Cl
Cl
Cl
Cl
Figure 1.7. AlF6 octahedron and AlCl3 dimer
1.4.4 Simple Organometallic Chemistry of the Group 13 Elements
The organometallic chemistry of the group 13 elements dates back to the middle 18th
century with the isolation of the sesquihalides of aluminum, which are mixtures of mono- and di-
ethylaluminum halides, (C2H5)AlI2 and (C2H5)2AlI. Today group 13 organometallic chemistry is
quite developed, thus all aspects cannot be addressed; however, a discussion on the extensively
studied simple R3M compounds (R = alkyl, aryl; M = group 13 metal) provides some seminal
discoveries of this chemistry.
All R3M (R = alkyl) are pyrophoric liquids with the exception of trimethylindium, Me3In,
which forms colorless crystals.29 They are well-established and some are even commercially
available. While most of the heavier trialky-group 13 compounds (Ga, In, Tl) are monomeric in
solution, trialkylindium and thallium compounds form tetrameric aggregates in the solid state.
Me3Al and Et3Al, on the other hand, are dimeric, [AlMe3]2,30 and contain bridging alkyl 3c-2e
bonds between two aluminum atoms. When first hypothesized, the 3c-2e bonding model for
AlMe3 was highly controversial,31,32 however spectroscopic evidence supports its dimeric nature.
In particular, this was corroborated by 1H NMR experiments, in which the single broad signal
that was observed for Me3Al at room temperature separated into two distinct signals at -70˚C,
17
evidence of two different chemical environments. The single crystal X-ray structure of
trimethylaluminum unambiguously confirms its structure.33
Due to their Lewis acidity, trialkylaluminum compounds are very useful as co-catalysts
in Ziegler-Natta olefin polymerizations. For this reason, they are produce in large-scale by a
process known as hydroalumination, which involves reaction of aluminum metal with terminal
olefins in the presence of hydrogen gas at elevated temperatures and pressures (Eq. 1.10).
2 Al + 3H2 + 6 RCH=CH2 2 (RCH2CH2)3Al (1.10)
Trialkylaluminum compounds also have utility as alkylating agents, usually transferring
only one alkyl group. Ligand transfer is also a convenient method to covert trialkylgalliums and
indiums into mono- and di-alkyl-group 13 halides, R2EX and REX2, respectively, by
disproportionation reactions with EX3 (E = group 13 metal, X = halides) (Eq. 1.11).30
R3E + 2 EX3
3 REX2
2 R3E + EX3 3 R2EX
or
The organometallic chemistry of gallium is not so dissimilar from that of aluminum.
Perhaps, the most interesting difference is that organogallium chemistry usually precludes 3c-2e
bonding that is commonly observer in organoaluminum chemistry. Gallium can be perfectly
stable with only a sextet of electrons. The first organogallium compounds, Et3Ga and
Et3Ga(OEt2), were prepared by Dennis in 1932 and spawned the genesis of the organogallium
chemistry.34 While triethylgallium, Et3Ga, was prepared by a redox reaction of diethyl mercury,
(1.11)
18
Et2Hg, with metallic gallium (Eq. 1.12), triethylgallium etherate, Et3Ga(OEt2) was obtained by a
metathesis reaction of ethylmagnesium bromide, EtMgBr, with GaBr3 in diethyl ether
(Eq.1.13).35
3 HgEt2 + 2 Ga165°C, 200 hr
2 Et3Ga + 3 Hg (1.12)
3 EtMgBr + GaBr3Et2O, -196°C
Et3Ga•Et2O + 3 MgBr2 (1.13)
The early endeavors into trialkyl-group 13 chemistry led to the inevitable investigations
of triaryl-group 13 compounds, Ar3E.36-39 Largely these compounds are monomeric, and unlike
their trialkyl-group 13 counterparts, donor molecules are seldom incorporated into their
structures due to the favorable steric and electronic effects afforded by the aryl substituents.
Steric factors in particular have profound implications on bonding and structure in
triarylaluminum compounds. For instance, triphenylaluminum, Al2Ph6, (Fig. 1.8) is dimeric with
two Al–C–Al bridges about tetrahedral aluminum centers, whereas trimesitylaluminum, Mes3Al
(Mes = 2,4,6-Me3C6H2), (Fig. 1.8) is monomeric with the three ligands configured in a propeller-
like arrangement about a trigonal planar aluminum atom. Steric considerations have now been
well-recognized in low-valent group 13 organometallic chemistry. Indeed, it has been
demonstrated that minor changes to ligand steric effects can have a great impact on structure and
bonding.
19
Al AlC6H5C6H5
C6H5C6H5
Al
Figure 1. 8. Structures of [Ph3Al]2 and (Mes)3Al
1.5 Sterically Demanding m-Terphenyl Ligands
Sterically demanding ligands have played a prominent role in the development of group
13 organometallic chemistry. The innate ability to kinetically stabilize low-valent main group
species by inhibiting decomposition pathways is a desirable characteristic that is often utilized to
obtain compounds with main group metal metal bonds. The m-terphenyl class of ligands is
prolific in this regard. Hart and coworkers developed a one-pot synthesis of m-terphenyls by
reaction of 2,6-dibromoiodobenzene with an arylmagnesium halide, ArMgX (Eq. 1.14).40
Although this reaction protocol provided m-terphenyls in good yield, the laborious preparation of
the starting materials, primarily 2,6-dibromoiodobenzene, presented a less than desirable reaction
scheme. Hart later published an improved synthesis for m-terphenyls by reaction of n-BuLi with
1,3-dichlorobenzene followed by addition of an aryl magnesium halide reagent. Quenching the
reaction with iodine affords the 1-iodo-m-terphenyl derivative in good yield (Eq 1.15).41 This
simple preparative procedure, however, is limited to symmetrical m-terphenyls.
20
Br
I
Br
+ ArMgX
Ar
I
Ar
(1.14)
Cl Cl
n-BuLi
Cl Cl
LI
3 ArMgX
Aryl
MgX
Aryl
I2
Ar
I
Ar
(1.5)
This protocol can be extended to an array of aryl groups but largely those with ortho
substitution have been chosen to study in low-valent main group organometallic chemistry. The
steric properties of these ligands are decidedly dominated by the degree substitution at this
position, and it appears that the isopropyl functionality is optimal for steric loading. It has been
shown that introduction of more bulky tert-butyl groups creates exceedingly close C H contacts
with the metal centers,42 causing excessive steric pressure that can often lead to undesirable side
reactions such alkyl group transfer to the metal center or insertion reactions via C H bond
activation.43 Three notable m-terphenyl ligands are shown in Figure 1.9.
2,6-Mes2C6H3- 2,6-(2,6-i-Pr3C6H2)2C6H3- 2,6-(2,4,6-i-Pr3C6H2)2C6H3-
Figure 1. 9. Structures of three common m-terphenyl ligands
21
The degree of substitution on m-terphenyl ligands has profound implications on the
structure and bonding of the respective organometallic complexes. Even the simple bis(m-
terphenyl)gallium halides, R2GaX (R = m-terphenyl; X = halide), are dramatically affected by
the steric properties of the ligand. For example, the coordination environment around the gallium
center in (2,6-Ph2C6H3)2GaI is distorted trigonal planar with a C Ga C bond angle of
134.3(3)°,44 while the more sterically imposing (2,6-Mes2C6H3)2GaX (Mes = 2,4,6-Me3C6H2-, X
= Cl,45 Br46) compounds assume a “T-shaped” gallium coordination sphere with C Ga C bond
angles of 153.5(5)°. This bond angle is nearly 20° larger than the corresponding bond angle in
(2,6-Ph2C6H3)2GaI and a substantial larger (33.5°) than the 120° anticipated for trigonal planar
geometry. It is noteworthy that the sterically more imposing bis(m-terphenyl)gallium halide (2,6-
(2,4,6-i-Pr3C6H2)2C6H3)2GaX (X = halide), with isopropyl functionally at the ortho-position of
outer phenyl rings, has not been isolated. The added steric encumbrance may be too great to
accommodate two of these large ligands about the gallium atom.
The substituents at the para position of the flanking phenyl rings also play a significant
role in the structure and bonding. Power and coworkers demonstrated that when ArLi (Ar = 2,6-
(2,4,6-i-Pr3C6H2)2C6H3-) is allowed to react with In(I)Br a monovalent indium diyl, ArIn:,47 is
produced in both solid and liquid states; however, utilizing a modified ligand, wherein the para-
isopropyl group is absent from the flanking phenyl rings, the indium diyls are permitted to
dimerize in the solid state to produce a compound with a formal indium indium double bond
(diindane), Ar´InInAr´, (Ar´ = 2,6-(2,6-i-Pr2C6H2)2C6H3-).48 Substituents on the central phenyl
ring may also alter structure and bonding in compounds containing main group metal metal
bonds. For example, the Sn Sn bond distance (2.6675(4) Å) in Ar´SnSnAr´49 (Ar´ = 2,6-(2,6-i-
Pr2C6H2)2C6H3-) is 0.4 Å shorter than that in the analogous compound, Ar˝SnSnAr˝ (Ar˝ = 2,6-
22
(2,6-i-Pr2C6H2)2-4-SiMe3-C6H2-),50 with the ligand having a trimethylsilyl group at the para-
position of the central phenyl ring. The trans-bent core of Ar´SnSnAr´49 also had a significantly
larger Sn Sn C bond angle (125.24(7)°) when compared to that in Ar˝SnSnAr˝ (99.25(14)°). The
authors attributed these structural changes to electronic differences between the two ligands. In
effect, addition of the SiMe3 ligand to the central phenyl ring changes the electronic character of
the Sn atoms enough that the small energy difference between two structures is surmounted.
Thus, not only is the degree of steric (i.e. Me, i-Pr, t-Bu) substitution important, but also its
location on the m-terphenyl ligand, as steric and electronic properties of the ligand are ultimately
transferred to the metal and contributes to structure and bonding.
1.6 Main Group Metal Metal Multiple Bonding
Compounds with C C single and multiple bonds are ubiquitous, and the literature, in
general, is replete with reports of compounds containing homonuclear and heteronuclear multiple
bonds of the second row elements (C, N, O). In contrast, the development of the analogous
chemistry of the heavier main group elements has only emerged over the last 30 years. Perhaps
the early prognostications by Pitzer51,52 and Mulliken22 which predicted, “…elements whose
principle quantum number is equal or greater than three were not capable of forming multiple
bonds…”, further discouraged investigations into this realm of chemistry. Notwithstanding this
bleak prospect for main group metal metal multiple bonding, in 1976 Lappert and coworkers
isolated and unambiguously characterized a compound containing the first Sn=Sn double bond
(distannene), R2Sn=SnR2 (R = CH(SiMe3)2)53 and proved that the heavier main group congeners
were indeed capable of multiple bonding. The structure of the first distannene contained two
pyramidal Sn atoms of trans-bent geometry with a Sn=Sn bond distance of 2.768(1) Å, which
23
was shorter than that found in elemental tin (2.80 Å). The key to the stabilization of this
intriguing compound was the considerable steric bulk and attractive electronic properties
inherent to the ligands.
Following this seminal discovery the strategy of employing sterically demanding ligands
to stabilize compounds containing main group metal metal multiple bonds was promptly
embraced. Early investigations in this regard were focused on the heavier main group
metal metal double bonds (dimetallenes) of the group 14 elements, R2E=ER2 (R = alkyl or aryl;
E = Si,54,55 Ge,56 Sn,53 Pb57), and group 15 elements, RE=ER (R = alkyl, aryl; E = As,58-60
Sb,60,61 Bi60,62). The group 13 congeners RE=ER (E = Ga,63 In;48 R = 2,6-(2,6-i-Pr2C6H3)2C6H3-),
have only recently been experimentally realized. The / bonding mode for ethene can be
applied well for the group 15 dimetallenes; however, less so as the column descends because the
-bond gradually weakens due to enhanced s-character. The group 15 dimetallenes begin to
resemble more of a E E single bond with n-electron pairs localized at the metal centers.
Computational studies have suggested that group 15 dimetallenes possess stronger -bonding but
weaker -bonding when compared to their group 14 congeners. 64 The smaller size of pnictogens
and interatomic electronic repulsion of the lone pairs found in group 15 dimetallenes may
contribute to this affect. 64
The bonding model for the group 1365,66 and 1464 dimetallenes is fundamentally different
from that of the second row elements, which is clearly demonstrated by their trans-bent
geometries. This variance from the first row elements is attributed to the lowering of the - *
energy gap as the column descends, which permits orbital mixing. As the metals acquire more s-
character and concomitant formation of non bonding electron pairs, the p p -bond weakens. In
essence, the group 13 and 14 dimetallenes are formed in the solid state by weak association of
24
two RM: units through donor-acceptor bonds. If the trend for carbon is referenced, the group 13
and 14 metallic double bonds are comparatively weaker and longer than expected as a
consequence of this unique bonding mode. As an illustrative example of this weak association,
distannene is a dimer of two R2Sn: units in the solid state, wherein a lone pair of electrons
residing in the sp2 -hybridized orbital of a discrete R2Sn: unit donates into the empty p-orbital of
another R2Sn: moiety (Fig. 1.10), however in solution, the weakly held dimers readily dissociate
into stannanediyl monomers (R2Sn:). This dimerization is responsible for the trans-bent
geometries of the dimetallenes. The out-of-plane angles ( ° E E R) become more
perpendicular, with respect to the E=E bond, as the column descends and has become somewhat
of a visual indicator of E E bond strength. Large out-of–plane angles correlates to higher bond
dissociation energies.
R
RSn
R
RSn
SnR
R
Solution
5sp2
Sn Sn
R
R
R
R
Solid state
Figure 1.10 Depiction of dissociation/dimerization in solution and solid states and donor-acceptor bonding model for R2Sn=SnR2 (R = -CH(SiMe3)2)
1.6.2 Group 13 Metal Metal Bonds
Reports of compounds possessing group 13 double bonds, RE=ER (E = Ga,63 In;48 R =
2,6-(2,6-i-Pr2C6H3)2C6H3-), have only been established this decade. In fact, the aluminum
analogue remains elusive. However, it is worth mentioning that the product of a suspected [2+4]
25
Diels-Alder cycloaddition reaction between toluene and a dialuminene intermediate, RAl=AlR,
suggests a transient Al=Al double bond.67
The lag in development of the organometallic chemistry involving group 13 multiple
bonds is not surprising since the first purported compound containing an Al Al single bond was
first reported in 1976,68 yet this account was dubious as it lacked vital single crystal X-ray
structural analysis. It would be twelve years later (1988) that Uhl prepared the first structurally
characterized compound containing a group 13 metal metal bond,
tetrakis[bis(trimethylsilyl)methyl]dialane, R2Al AlR2 (R = -CH(SiMe3)2) (Al Al = 2.660(1) Å)
(Fig. 1.11), by potassium reduction of R2AlCl (Eq. 1.16 ).69 Soon thereafter, Uhl also prepared
the analogous digallane, R2Ga GaR2 (R = -CH(SiMe3)2) (Ga Ga =2.541(1) Å), by allowing RLi
to react with Ga2Br4•(dioxane)2 (Eq. 1.17).70 This simplistic approach was ingenious, as the
staring material, Ga2Br4•(dioxane)2, already contained a Ga Ga single bond, and the task simply
became addition of the ligands while maintaining the labile bond. Utilizing a similar protocol,
Uhl also synthesized the first diindane, R2In InR2 (R = -CH(SiMe3)2),71 and thus completed the
series of compounds containing the first group 13 E E single bonds (Eq. 1.18). Notably, all of
these compounds were isostructural, consisting of a planar C2E-EC2 core of two sp2 hybridized
group 13 metals bound together. The two proximal empty p-orbitals on the group 13 metals can
readily accept an additional electron from lithium to give radical anions [R2E ER2]·- (E = Ga,72
Al73) with short E E bond distances (Al = 2.53 Å; Ga = 2.40 Å) and bond orders of 1.5.
2 KAl Al
R
R
R
R2 R2AlCl
-2 KCl
R = -CH(SiMe3)2 (1.16)
26
Ga2Br4•(dioxane)2 + 4 RLi-4 LiBr
Ga Ga
R
R
R
R
R = -CH(SiMe3)2
In2Br4•(TMEDA)2 + 4 RLi-4 LiBr
In In
R
R
R
R
R = -CH(SiMe3)2
Figure 1.11. Molecular structure of tetrakis[bis(trimethylsilyl)methyl]dialane, R2Al AlR2
1.6.3 Main Group Metal Triple Bonds
The more ambitious task of synthesizing heavier main group triple bonds (dimetallynes),
R-E E-R, was pursued utilizing an array of sterically imposing ligands. From the onset, the
classification and description of dimetallynes was difficult to assess because the structure and
bonding of these heavier alkyne analogues is significantly different from that of carbon triple
bonds. Whereas a classical /2 model adequately depicts multiple bonding for the first row
elements, the bonding mode of the heavier group 14 alkyne analogues departs from this
(1.17)
(1.18)
27
conventional description. Instead, the triple bonds of heavier analogues are essentially identical
to that put forth for the distannene (two donor-acceptor bonds) (Fig. 1.10), but are augmented by
an additional p p -bond (Fig. 1.12). This bonding arrangement results in a “slipped” or “trans-
bent” triple bond, as opposed to linear, and has been a common structural manifestation for all
dimetallynes isolated to date (Ga,21 Al,74 Si,75 Ge76,77, Sn,49 Pb78).
R
R
-bond
donor-acceptor bond
donor-acceptor bond
E E
R
R
Figure 1.12. Bonding model for the heavier main group metallynes
One example of the perplexity of assigning “triple bond” nomenclature to the heavier
analogues is easily found in the description of RPbPbR (R = 2,6-(2,6-i-Pr2C6H3)2C6H3-),78 which
was stated as “the first stable heavier group 14 element analogue of an alkyne”. Indeed, it was
the first report of a group 14 compound with a general formula of REER, however the Pb–Pb
bond distance (3.1881(1) Å) was significantly longer than the average Pb Pb (diplumbanes)
single bond distances (2.85 Å av.) found in Ph3Pb–PbPh379 and Ph3Pb–Pb(p-tol)3.
80 Subsequent
computational studies on model diplumbylenes, RPbPbR (R = H, Ar), suggested that the dihedral
angle of the trans-bent Pb–Pb–C core (~90°) was a result of a non-bonding pair of electrons on
each lead atom. Thus, the claimed experimental Pb Pb triple bond was merely a novel Pb–Pb
single bond.81
28
This discussion would be remiss if the gallium alkyne analogue were not discussed
because the synthesis and isolation of the first digallyne, Na2[RGa GaR] (R = 2,6-(2,4,6-i-
Pr3C6H2)2C6H3-) (Fig. 1.13),21 by the Robinson group, was a monumental, yet provocative,82,83
achievement. As with all new concepts that challenge conventional wisdom, the nature of the
Ga–Ga bond sparked a spirited debate that was contested84-86 and defended66,87-91 with volleying
reports. Objections to the formulation of a triple bond were founded on fundamental issues
regarding structure and bonding, i.e. the Ga–Ga bond distance of 2.319(3) Å, the trans-bent C–
Ga–Ga–C array, and the Wiberg Bond Index (WBI) bond order of 1.13. Although the Ga–Ga
bond distance is the shortest on record, it is only marginally shorter than Ga–Ga single bond
distances reported for other relevant compounds (2.395-2.778 Å).22,70,72,92-94 Notwithstanding, the
Ga–Ga bond distance of the digallyne is shorter than twice its covalent radii (2.42 Å).
Furthermore, it seems that the implicit presumption that increased bond multiplicity correlates to
a net decrease in bond length is a concept that is reserved for carbon. For example, the Pb=Pb
double bond distance (3.0515(3) Å) in RPb=PbR (R = 2,4,6-i-Pr3C6H2-)57 is more than 0.2 Å
longer that the average Pb–Pb single bond distances (2.85 Å) in Ph3Pb–PbPh379 and Ph3Pb–Pb(p-
tol)3.80 The longer Pb=Pb bond distance was never a factor to challenge its validity as a double
bond. Moreover, E=E bond distances in the heavier group 14 dimetallenes, R2E=ER2 (E = Si, Ge,
Sn), are only marginally shorter than those of their respective dimetallanes R3E-ER3.64
The trans-bent geometry of the C–Ga–Ga–C core seems to be a futile objection to the
formulation of the gallyne; as previously discussed, this seems to be a common geometry for all
of the heavier main group alkyne analogues. Finally, pertaining to the WBI values for the gallyne
(1.13), it is granted that the Ga Ga triple bond in the digallyne is weaker because of the unique
bonding mode for the dimetallynes, however it should also be considered that WBI bond order
29
values are commonly smaller than the formal bond order values. Even for simple and well-
established compounds such as HF and H2O, the WBI bond orders are significantly lower than
1.0 (0.67 and 0.76, respectively). Clearly, these compounds contain “true” single bonds!
Ga Ga
Na
Na
Figure 1.13. Schematic depiction and single crystal X-ray structure of gallyne, Na2[RGa GaR]
(R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-)
To date, the chemistry community has accepted the triple bond formulation for the
digallyne. The recently reported isoelectronic/isostructural aluminum analogue of the gallyne by
the Power group,74 in which the term “dialuminyne” was used to evoke the connotation of an
aluminum aluminum triple bond, strengthens the argument for the gallyne triple bond
formulation. If the “dialuminyne” is regarded an aluminum–aluminum triple bond, shouldn’t the
digallyne garner the same consideration?
30
1.6.2 Group II and 12 Metal Metal Bonding
Recently there has been a surge of activity in the quest to synthesize compounds with
group II and group 12 metal metal bonds. The major obstacle in producing compounds with
metal metal bonds of these divalent elements is stabilizing the +1 oxidation state and protecting
the coordination spheres from donor molecules. Although the +1 oxidation state for mercury is
well known, as well as reports of Hg–Hg bonds,95,96 there has been a paucity of reports of
compounds containing Zn or Cd metal metal bonds.97,98 Furthermore, reports of compounds
with group II (Be, Mg, Ca, Sr, Ba) metal–metal bonds were nonexistent. Fortunately, recently a
few unambiguously characterized compounds containing group II and group 12 metal metal
bonds have been reported.
Organomagnesium chemistry has been extensively studied; hence it is surprising that a
molecular species containing an Mg–Mg bond was not isolated earlier. Although it has been
proposed that dimagnesium complexes RMgMgX (R = CH3, H; X = halide) with “strong”
Mg Mg bonds are generated in production of Grignard regents99 and that a dimagnesium
species, HMgMgH, is detected in matrices;100 an unambiguously characterized compound
containing a Mg–Mg bond remained more of an curiosity than reality for sometime. Ultimately,
Jones101 and coworkers synthesized the first stable dimagnesium compounds containing
metal metal bonds using bulky guanidinate and -diketiminate ligands to protect the labile bond,
[Mg(Priso)]2 (Priso = [(Ar)NC(N-i-Pr)N(AR)]-; Ar = 2,6-i-Pr2C6H3-), and [Mg(nacnac)]2
(Nacnac = [{(2,6-Pri2C6H3)N(Me)C}2CH)] (Figure 1.14).101 Surprisingly, the Mg–Mg bond
distances in these compounds (2.8508(12) and 2.8457(8) Å, respectively) are longer than the sum
of two magnesium covalent radii (2.72 Å), yet are shorter than those of diatomic or elemental
magnesium. These compounds are the only specimens that contain group II metal metal bonds.
31
N
N
Mg
Ar
Ar
Mg
N
N
Ar
Ar
N
N
Mg
Ar
Ar
N
N
Mg
Ar
Ar
Ar = 2,6-i-Pr2C6H3
Figure 1.14. Structures of [Mg(Priso)]2 and [Mg(Nacnac)]2
Carmona and coworker’s unexpected isolation of decamethyldizincocene, Zn2( 5-
C5Me5)2, by reaction of Zn(C5Me5)2 with diethyl zinc, Zn(C2H5)2, (Eq. 1.19) was the first
structurally characterized compound containing a Zn Zn bond.102 The structure of this
fascinating compound displayed two pentamethylzincocene fragments, Zn( 5-C5Me), bound
together by a linear Zn–Zn bond. Indeed, the most striking feature of this compound was the
short Zn–Zn bond distance (2.305(3) Å), which was shorter than twice the Pauling’s single bond
metallic radius (2.50 Å).
Zn
Zn
Zn + Zn(C2H5)2 +Zn
C2H5
(1.19)
This landmark discovery set the stage for further investigations into synthesizing
compounds with group 12 metal–metal bonds. Our group synthesized the second compound
containing a Zn Zn bond using a bulky -diketiminate ligand, RZn ZnR (R= [{(2,6-
Pri2C6H3)N(Me)C}2CH]),103 which had a Zn Zn bond distance of 2.3586(7) Å. This distance is
32
slightly longer than that in Zn2( 5-C5Me5)2 (2.305(3) Å), but still shorter than the sum of two Zn
covalent radii. The pursuit for compounds containing group 12 metal–metal bonds was
complemented with the isolation of the first structurally characterized compound containing a
Cd–Cd bond, RCd–CdR (R = 2,6-(2,6-i-Pr2C6H3)2C6H3-),104 followed by preparations of
isostructural Zn and Hg analogues (Figure 1.15).105
Ar
Ar
M M
Ar
Ar
M = Zn, Cd, Hg; Ar = 2,6-(i-Pr-C6H3)2C6H3
N
N
Zn
Ar
Ar
N
N
Zn
Ar
Ar
Ar = 2,6-(i-Pr-C6H3)2C6H3
Figure 1.15. Structures of compounds containing group 12 metal metal bonds
To end, initially it was deemed that metal metal bonding for the heavier main group
elements was impossible; today however, by utilizing sterically demanding ligands with
attractive steric and electronic effects, molecular species containing such bonds are known from
group 2 to group 15 elements. Furthermore, the structure and bonding of the heavier main group
multiple bonded species deviates greatly from that of carbon multiple bonds. In fact, one is
drawn to the reality that the characteristics of carbon multiple bonding are an exception rather
than the rule. Finally, with the recently synthesized compounds containing Mg Mg bonds, the
continuation for the molecular species containing main group metal metal bonds will
undoubtedly be focused on the remainder of group II elements.
33
1.7 Metalloaromaticity
Aromaticity has been traditionally described as a number of Hückel’s 4n + 2 -electrons
delocalized in a planar cyclic structure that results in enhance stabilization energy greater than
that of conjugation alone. It is encountered early on in chemical scholarship. To avoid confusion
the concept is routinely explained in simple terms and enforced with strict stipulations that act as
litmus tests to readily recognize aromaticity. This early training is further augmented with
unambiguous examples of aromatic compounds, which are carbon-based molecules with
inclusion of O, S, and N. Though this early instruction may serve well to simplify aromatic
characteristics, in reality subtle intricacies of aromaticity can be difficult to assess with these
rudimentary principles. In some instances, novel compounds exhibiting unusual aromatic
properties can be difficult to appraise based solely on physical, structural, and chemical
properties. Because aromaticity cannot be measured quantitatively, new theoretical techniques
such as Nucleus-independent Chemical Shifts (NICS),106-108 which utilizes geometrical sensitive
magnetic criteria, have been developed to further aid in deciphering aromaticity.
Indeed, aromaticity has transcended its initial boundaries of carbon and its neighbors and
has been observed in compounds containing transition and main group metals. The first of these
metallic aromatic compounds can be traced to the study of the enhanced stability of the
antiaromatic cyclobutadiene ligand (Cb) in CbFe(CO)3 (Fig.1.16) by Bursten,109 which
ultimately proposed that traditional aromatic behavior is induced into the Cb ring by an Fe C4H4
-interaction. The term metalloaromaticity was used to describe the unique and unprecedented
bonding scenario.
34
Fe
C
C
C
O
O
O
Figure 1.16. Schematic depiction of CbFe(CO)3
The literal connotation of metalloaromaticity wherein all-metallic ring systems exhibit
aromatic behavior was first experimentally realized by the Robinson group with the synthesis
and isolation of the cyclotrigallenes, M2[GaR]3 (M = Na,24 K,25 R = 2,6-Mes2C6H3, Mes = 2,4,6-
Me3C6H2-) by alkali metal reduction of RGaCl2.46 The cyclotrigallenes consist of an essentially
equilateral triangular arrangement of three trigonal planar gallium atoms (Ga Ga Ga bond angle
~ 60°) with two alkali metal cations resting above and below the Ga3-ring. The Ga Ga bond
distance in the cyclotrigallenes average 2.43 Å and is slightly shorter than an average Ga Ga
single bond distance (~2.5 Å) (Fig. 1.17).
Ga
Ga
Ga
2 e-
Figure 1.17. Schematic depiction and single crystal X-ray structure of tricyclogallene, Na[GaR]3
35
The cyclotrigallenes are comparable to the isoelectronic cyclopropenium ion, R3C3+, in
that both are 2 -electron aromatic species albeit in a different mode. While R3C3+ affords
delocalization of two -electrons of an olefin segment through an carbocation, the
tricyclogallenes gain aromaticity by delocalizing two electrons donated from the alkali metals
into the cyclic array of empty p-orbitals on the three proximal gallium atoms. This affords an -
electron cloud above and below the Ga3-ring (Fig. 1.18). It should be noted that the alkali metals
are not close enough to engage in metal metal bonding with the gallium atoms, but they are
integrally assimilated in the structure of the tricyclogallenes. Moreover, the characteristic
features of aromaticity were adequately displayed in the cyclotrigallenes, i.e. bond length
equalization, aromatic stabilization energies, and magnetic susceptibility exaltations.
Computational studies also supported the existence of a ring current through NICS calculations
(-45.4 ppm) on a model cyclotrigallene, [H3Ga3]2-.106
It should also be noted that the isoelectronic tricycloaluminene, [R3Al3]Na2 (R = 2,6-
Mes2C6H3), has also been synthesized. Its structure and bonding parallels that of the
cyclotrigallenes.74
Figure 1.18. Orbital description of [H3Ga3]2- showing HOMO -electron cloud above and below
the Ga3-ring
36
Aromaticity can be very subtle as traditional constraints become evermore irrelevant. A
prime example of this is apparent in the unsuspecting aromatic species, K2[Ga4R2] (R = 2,6-
(2,4,6-i-Pr3C6H2)2C6H3) (Fig. 1.19),22 which contained an essentially square planar Ga4-ring
comprised of two “naked” gallium atoms with a singlet pair of electrons and two of them ligated.
This compound also possessed two potassium atoms that resided above and below the Ga4 plane,
slightly favoring the opposing ligand substituted gallium atoms. The Ga Ga bond distances were
virtually equivalent at 2.46 Å.
Unfortunately, the purpose of this report was to denounce the formulation of the gallyne
by showing that the alkali metals contribute significantly to its structure and bonding and
disregarded a more important property of this compound metalloaromaticity. The aromatic
properties of this compounds were not reported until three years after its initial report.65 Quite
surprisingly, quantum chemical calculations showed that this compound was not only a 2 -
aromatic system, but simultaneously it was also -antiaromatic in terms of electron counting
(eight total electrons).110 This uniquely stunning result further signified the conflicting nature of
aromaticity.
Ga
Ga Ga
Ga
2 e-
Figure 1.19. Structure of [Ga4R2]2- ( R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-)
37
The dianionic tetragallium compound, Na2[Ga4R4](THF)2 (R = t-Bu3Si-) (Fig. 2.20), is
perhaps the unlikeliest compound to exhibit metalloaromaticity.111 Several structural features of
this compound are counterintuitive to aromaticity, i.e., the Ga4 ring is puckered in a butterfly
conformation and the Ga Ga bond distances differ in an alternating fashion (2.4238(6) and
2.416(1) Å), yet the authors deduced it to be a 2 -electron aromatic system. The non-planarity of
the ring was dismissed as a consequence of ligand steric interactions of the supersilyl groups,
while the alternating Ga Ga bond lengths were viewed as menial distortions. They, however,
described the compound by two different modes of bonding. In one description, the two Na
atoms donate their one electron entirely to the Ga4 cluster, resulting in the prescribed 2 -electron
aromatic system. In an alternate formulation, the two Na atoms transfer their electron only
partially and become an integral part of the structure by Ga Na metal metal bonding, resulting
is a 10-electron Ga4Na2 cluster that is consistent with Wade-Mingos 2n +2 cluster electron rules.
112,113 As of yet, there has not been a careful theoretical investigation on the aromatic properties
of this compound to discern rather which of the two different bonding possibilities are correct.
Ga
Ga
GaGa
RR
R
R Na
Na
THF
THF
R = t-Bu3Si-
Figure 1.20. Structure of Na2[Ga4R4](THF)2 (R = t-Bu3Si-)
38
In conclusion, group 13 compounds that display metalloaromaticity are few, yet comprise
of interesting and varied structural arrays. The prevailing characteristic has been electron
donation from alkali metals that allow for delocalization through a cyclic arrangement of the
proximal group 13 unoccupied p-orbitals. Furthermore, these compounds have shown that
aromaticity can be unexpected, and may be overlooked if not thoroughly examined.
39
CHAPTER 2
RESULTS AND DISCUSSIONS
2.1 Syntheses and Structures of Less-sterically Demanding
m-Terphenyl Group 13 Complexes
2.1.1 Introduction
The organometallic chemistry of low-valent group 13 species has long been a focus for
this laboratory. In particular, reductions of m-terphenyl-group 13 halides, REX2 (R = m-
terphenyl, E = group 13 element, X = halide) have been an effective strategy to synthesize
compounds containing metal metal bonds. Studies have shown that by manipulating the
electronic and steric properties of the m-terphenyl ligand, the structure and bonding of a given
organometallic compound or complex may be dramatically altered. Since the bulkiest of these
ligands, 2,6-Mes2C6H3-, 2,6-(2,6-i-Pr2C6H2)2C6H3-, 2,6-(2,4,6-i-Pr3C6H2)2C6H3-, have been
extensively examined for their ability to kinetically stabilize complexes possessing main group
metal metal bonds, we set out to gain further insight into the significance of ortho-substitution,
or the lack thereof, on the flanking phenyl rings.
Two m-terphenyl ligands lacking ortho-substituents on the flanking phenyl rings, 2,6-(4-
t-BuC6H4)2C6H3- (R) and 2,6-(4-Me-C6H4)2C6H3- (R´), were examined on group 13 halides to
ascertain the stability and structural properties of their respective ligand–metal complexes and
later evaluated on their ability to stabilize group 13 metal metal bonds. Structural
representations of R and R´ are shown in Figure 2.1. From a steric aspect, these ligands are
deceptively similar, however electronically they differ significantly due to varied contributions
40
of -donor inductive effects afforded by the para-substituents, primarily due to enhanced
hyperconjugation of the t-butyl group versus methyl.
2,6-(4-t-BuC6H4)2C6H3- 2,6-(4-Me-C6H4)2C6H3-
RR
Figure 2.1. Structures of 2,6-(4-t-BuC6H4)2C6H3- (R), and 2,6-(4-Me-C6H4)2C6H3- (R´)
The respective 1-iodo-m-terphenyl derivatives (RI or R´I) are synthesized in good yield
by literature protocol (65-85%) (Refer to section 1.5 (Eq. 1.15) for a detailed scheme).41 A
modified lithiation procedure in hexane employing n-BuLi at -78°C affords the lithium
analogues (RLi or R´Li) as white to off-white powders in excellent yield (96-98%) (Eq. 2.1). The
lithium derivatives are sparingly soluble in diethyl ether, hexanes, and toluene, and form thick
slurries at -78°C. Though they are highly soluble in tetrahydrofuran at room temperature, fine
black particulate matter is formed on standing for short periods, suggesting some degree of
decomposition. However, placing the lithium derivatives at -78°C before addition of THF
appears to lessen decomposition.
RI or R In-BuLi, Hexane,
-78°CRLi or R Li
(2.1)
41
2.1.2 Syntheses of 2,6-Di(4-t-butylpheny)phenyl-Group 13 Complexes
Reactions of RLi (R = 2,6-(4-t-BuC6H4)2C6H3-) with group 13 salts (GaCl3, AlCl3, AlBr3,
InCl3) were performed in diethyl ether at -78°C. RLi was generally transferred to the respective
group 13 salts to control stoichiometry and avoid excessive ligation. Unless otherwise stated, all
of the m-terphenyl-group 13 complexes are air and moisture sensitive and were characterized by
single crystal X-ray crystallography, 1H NMR, elemental analysis, and melting point
determination.
Compounds 1-5 (RGaCl2(OEt2) (1), R2GaCl (2), RAlBr2(OEt2) (3), O[AlClR(OEt2)]2 (4),
R3In (5)) were obtained as colorless crystals by reaction of RLi (R = 2,6-(4-t-BuC6H4)2C6H3-)
with their respective group 13 halides (Eq. 2.2). These compounds have fairly high thermal
stabilities, however compound 5 is exceptional, melting above 288°C. While compounds 1-3
were prepared in a straightforward manner, the isolations of 4 and 5 were unexpected and
deserve special synthetic discussion.
In an attempt to synthesize R2AlCl, two equivalents of RLi were allowed to react with
AlCl3, instead the reaction produced an organometallic oxo-bridged-dialuminum chloride
etherate, O[AlClR(OEt2)]2 (4), (Eq 2.2). The reaction mechanism for the formation of 4 is not
well understood, however it appears that the reaction was either contaminated with trace amounts
of H2O, or the ethereal solvent was activated. The latter proposition may be ascribed to the
strong Lewis acid properties of AlCl3, which has been well documented as an ether cleavage
reagent.114 To eliminate the possibility of H2O incursion, the reaction was repeated as described
with a particular emphasis to restrict H2O exclusion. Nevertheless, a similar conclusion was
drawn as 4 was once again isolated. Similarly, switching to AlBr3 in place of AlCl3 provides the
isoelectronic/isostructural bromide analogue of 4.
42
RLi
GaCl3Et2O,-78°C
RGaCl2 Et2O (1)
R2GaCl (2)
RAlBr2 Et2O (3)
O[AlXR(OEt2)]2 (4)
R3In (5)
1/2 GaCl3Et2O,-78°C
AlBr3Et2O,-78°C
1/2 AlX3
Et2O,-78°C
X = Cl, Br
InCl3Et2O,-78°C
(Eq. 2.2)
The unexpected formation of R3In (5) by reaction of RLi with a slurry of InCl3 in a 1:1
ratio is intriguing. Even after several attempts, the anticipated 1:1 product, RInCl2, could not be
prepared. Perhaps the heterogeneous reaction conditions promoted the formation of 5, wherein
the more soluble RLi reacts multiply with the partially soluble InCl3. Interestingly, unlike
compounds 1-4, compound 5 can be handled in air without apparent signs of decomposition.
This is probably due to the substantial shielding afforded by the three bulky m-terphenyl ligands,
which envelop the indium atom.
43
2.1.3 Molecular Structures of 2,6-Di(4-t-butylpheny)phenyl Group 13 Complexes
Single crystal X-ray analysis of compounds 1-5 reveals an array of structurally interesting
molecules. Their structures are shown in Figures 2.2 2.6, respectively. Compounds 1 and 3 are
m-terphenyl group 13 etherates with tetrahedral metal centers, whereas 2 is a trigonal planar
bis(m-terphenyl) gallium chloride, and compound 4 is a rare oxo-bridged di(m-
terphenylaluminum chloride). Compound 5 compliments these complexes and is notable as the
first report of a tris(m-terphenyl) group 13 compound.
The structure of RGaCl2(OEt2) (1) (Fig. 2.2) reveals the first structurally characterized m-
terphenylgallium dihalide etherate, RGaX2(OEt2). Although RGaCl2(OEt2) (R = 2,6-(2,4,6-i-
Pr3C6H2)2C6H3-) was previously reported, no corroborating structural data was presented.115
Several structural features of 1 merit discussion. Specifically, the pseudo-tetrahedral geometry
around the four coordinate gallium atom in 1 is expressed by the large C(1) Ga(1) Cl(1) and
C(1) Ga(1) Cl(2) bond angles, 123.49(12)° and 118.72(13)°, respectively, which greatly exceed
the expected value for tetrahedral geometry (109.5°) and are more closely associated with
trigonal planar geometry. As anticipated, the remaining bond angles are smaller; however, the
O(1) Ga(1) Cl(4) bond angle (95.05(11)°) is unusually small.
Since 1 is the first structurally characterized m-terphenyl-gallium etherate, special
attention is drawn to the gallium ether interaction. As expected, the weak coordination of the
diethyl ether molecule in 1 creates a significant longer Ga(1)–O(1) bond distance (2.041(4) Å)
when compared to the Ga–O -bond distance (1.7833(17) Å) found in R2GaOH (R = 2,6-
Mes2C6H3-).116 For comparison purposes, the Ga O bond distance in 1 is also longer that the
bridging Ga–O–Ga bond distances (Ga O = 1.938(2) and 1942(2) Å) in [RGa(Cl)(μ-OH)]2.116
The Ga(1) C(1) bond distance (1.98(5) Å) in 1 is comparable to other m-terphenylgallium
44
dihalides (1.930(8) to 1.985(1) Å) on the high side of the range.44,46,117 The Ga(1) Cl(1) and
Ga(1) Cl(2) bond distances (2.205(2) and 2.1872(13) Å, respectively) are quite similar to the
terminal Ga Cl bond distance (2.290-2.172 Å) in the m-terphenylgallium dichloride dimer, [2,6-
Mes2C6H3GaCl2]2,46 but somewhat shorter than its bridging Ga Cl bond distances (2.333(5) and
2.324(4) Å).
The single crystal X-ray structure of the bis(m-terphenyl)gallium complex, R2GaCl (2)
(Fig. 2.3), reveals a three coordinate gallium atom in an seriously distorted trigonal planar
environment. The geometry about the gallium atom in 2 is consistent with that in (2,6-
Ph2C6H3)2GaI,44 but contrasts with the “T-shaped” coordination around the gallium center in the
similar (2,6-Mes2C6H3)2GaX (X = Cl,45 Br46) compounds. This is almost certainly the
consequence of steric hindrance in the latter. This can be placed in a simple perspective, wherein
the less bulky m-terphenyl ligands utilized in 2 and (2,6-Ph2C6H3)2GaI require significantly
smaller C(1)–Ga(1)–C(27) bond angles (137.37(12)° and (134.3(3)°), respectively) to
accommodate the two ligands, whereas the more sterically encumbered “T-shaped” bis(m-
terphenyl)gallium halides warrant a significantly wider C Ga C bond angle (153.5°) to lessen
steric interactions. Similar to previously reported bis-m-terphenyl galliums, the two m-terphenyl
ligands in 2 adequately shield the gallium center so as to preclude solvent coordination. The
Ga(1)–C(1) and Ga(1)–C(27) bond lengths in 2, 1.981(3) and 1.997(3) Å, respectively, lie in the
range (1.971(12) Å 1.988(6) Å and 1.984 Å) of most bis-m-terphenyl galliums;44,46 however, a
slight variance is detected in the two Ga C bond distances (2.001(16) and 1.956(16) Å) in (2,6-
Mes2C6H3)2GaCl, which places those in 2 somewhere in between. Interestingly, although 2 is
substantially less crowded than (2,6-Mes2C6H3)2GaCl, the Ga Cl bond distance in 2 (2.2537(10)
Å) is substantially longer (2.177(5) Å). The exact cause of this inconsistency is unclear.
45
Figure 2.2 Molecular structure of RGaCl2(OEt2) (1)
Table 2.1 Selected bond distances [Å] and angles [°] for RGaCl2(OEt2) (1)
Atoms Distance Atoms Angle Ga(1) C(1) 1.985(5) C(1) Ga(1) O(1) 105.89(15) Ga(1) O(1) 2.041(4) C(1) Ga(1) Cl(1) 123.49(12) Ga(1) Cl(1) 2.1872(13) C(1) Ga(1) Cl(2) 118.72(13) Ga(1) Cl(2) 2.2238(14) Cl(1) Ga(1) Cl(2) 106.70(6)
46
Figure 2.3. Molecular structure of R2GaCl (2)
Table 2.2 Selected bond distances [Å] and angles [°] for R2GaCl (2)
Atoms Distance Atoms Angle Ga(1) C(1) 1.981(3) C(1) Ga(1) C(27) 137.37(12) Ga(1) C(27) 1.997(3) C(1) Ga(1) Cl(1) 106.69(9) Ga(1) Cl(1) 2.2537(10) C(27) Ga(1) Cl(1) 115.76(9)
47
The structure of RAlBr2(OEt2) (3) (Fig. 2.4) is isoelectronic with RGaCl2(OEt2) (1). Both
structures are m-terphenyl group 13 etherates and share a common four-coordinate distorted
tetrahedral environment about the metal centers. Similar to that in 1, the C(1)–Al(1)–Br(1) and
C(1)–Al(1)–Br(2) bond angles, 117.46(15) and 120.10(15)°, respectively, are significantly
distorted from classical tetrahedral geometry, while the Br(1)–Al(1)–O(1) bond angle,
97.94(14)°, is much smaller than anticipated. There is one additional structural feature of 3 that
deviates from 1. Specifically, whereas in 1 the Cl–Ga–Cl bond angle (95.05(11)°) was the
smallest bond angle around gallium, the analogous Br(1)–Al(1)–Br(2) bond angle (107.22(6)°) in
3 is consistent with the anticipated value. This may be due to the larger atomic radius of
bromine, which would have greater electronic repulsion than chlorine. It is generally accepted
that with increasing steric crowding about a group 13 element the E C bonds lengthen due to
steric repulsion. Indeed, there is very little difference between the Al(1) C(1) bond distance
(1.979(5) Å) in 3 and that of the only other m-terphenylaluminum dibromide etherate,
Ph3PhAlBr2(OEt2) (Al C 1.983(5) Å), which are in terms of sterics are very similar. This trend is
also consistent when comparing the shorter Al(1) C(1) bond distance in 3 with that of the more
sterically encumbered 2,6-Mes2C6H3AlCl2(OEt2) (Al C 1.992(3)Å).118 However a break in this
concept is revealed when comparing the Al C bond distance in 3 with that of most sterically
encumbered m-terphenylaluminum halide isolated to date, RAlCl2(OEt2) (R = 2,6-(2,4,6-i-
Pr3C6H2)2C6H3-),118 which has a significantly shorter Al C bond distance (1.954(11) Å) than
that in 3. The authors suggested that this short bond distance is the result of a higher degree of
ionic character inherent to the Al C bond, thereby strengthening, and thus shortening, the bond.
Another subtle feature of 3 is that the phenyl ring plane is bent by 15.54° from coplanarity with
the Al C bond. This distortion may be due to packing forces in the crystal lattice, a factor that
48
allows for flexibility in the ionic Al-C bond.118 In general, the bond distances in 3 are as
expected, however the Al(1)–Br(1) and Al(1)–Br(2) bond distances (2.3175(17) Å and
2.3010(16) Å, respectively) differ slightly but both are similar to those in RAlBr2·OEt2 (R =
2,4,6-Ph3C6H2) (2.297(3) and 2.302(3) Å).118 These bond distances in 3 are also comparable
with the terminal Al Br bond distance (2.285(6) Å) in [RAlBr3Li]2, (R = 2,6-Mes2C6H3),119 but
are substantially shorter than those with lithium interactions (2.359(5) and 2.398(5) Å). The
anionic nature of [RAlBr3Li]2 may also be partially attributed to the longer Al Br distances.
Figure 2.4. Molecular structure of RAlBr2(OEt2) (3)
Table 2.3 Selected bond distances [Å] and angles [°] for RAlBr2(OEt2) (3)
Atoms Distance Atoms Angle Al(1) O(1) 1.877(4) O(1) Al(1) C(1) 106.64(19) Al(1) C(1) 1.979(5) C(1) Al(1) Br(2) 120.08(15) Al(1) Br(2) 2.3013(16) C(1) Al(1) Br(1) 117.46(15) Al(1) Br(1) 2.3173(17) Br(2) Al(1) Br(1) 107.22(6)
49
The crystal structure of O[AlClR(OEt2)]2 (4) (Fig. 2.5) is as interesting as its peculiar
formation. The structure displays two four-coordinate aluminum atoms connected by an oxygen
bridge and each is covalently bound to an m-terphenyl and chloride ligand. The tetrahedral
aluminum coordination spheres are completed with diethyl ether coordination. It is interesting to
note that compound 4 has no counterpart in the literature, however there is one closely related
compound, [RAlCl(μ-OH)]2 (R =2,6-(2,4,6-i-Pr3C6H2)2C6H3-),119 which contains two bridging
hydroxide and terminal chloride ligands on each aluminum atom.
An unusual structural feature of 4 may be viewed along the Al(1) O(1) Al(2) vector,
which shows a “gauche-type” configuration of the m-terphenyl ligands with a torsion angle of
58.66°, while the chloride ligands are assume almost an “anti” conformation (Cl Al Al Cl
torsional angle, 154.57°), and the diethyl ether molecules are coordinated to the aluminum atoms
in more of a “gauche-like” conformation (torsion angle = 62.56°). A schematic depiction of these
phenomena is better illustrated by the Newman projection shown Figure 2.6. Considering the
steric bulk of the ligands, it is surprising that this conformation observed for 4 is preferred, as
one might expect the ligands to be arranged on opposite sides of the molecule to lessen steric
interactions. In fact, upon closer examination of the molecular structure of 4 shows that there are
several close intramolecular C H···H C contacts between the two ligands (2.74 Å shortest).
These contacts are well within range of van der Waal forces of attraction (3.44 Å), however it
doubtful that these weak forces (5-7 kJ/mol) are responsible for these unexpected structural
features.
50
Figure 2.5. Molecular structure of [RAlCl(OEt2)]2O (4)
Table 2.4 Selected bond distances [Å] and angles [°] for [RAlCl(OEt2)]2O (4)
Atoms Distance Atoms Angle Al(1) O(1) 1.696(4) Al(2) O(1) Al(1) 160.0(2) Al(1) C(1) 2.001(5) O(1) Al(1) Cl(1) 108.85(15) Al(1) Cl(1) 2.354(2) C(1) Al(1) Cl(1) 117.90(17) Al(2) O(1) 1.691(4) O(1) Al(2) Cl(2) 110.77(14) Al(2) C(31) 2.013(5) C(31) Al(2) Cl(2) 114.45(15) Al(2) Cl(2) 2.3939(19) O(1) Al(2) C(31) 120.68(19)
51
Atoms assimilated for torsion angle Torsion angle (deg)
R-Al…Al-R 58.66
Cl-Al…Al-Cl 154.57
Et2O-Al…Al-OEt2 62.56
Figure 2.6. Table for torsion angles (deg) and Newman projection of 4: “looking down the
Al O Al vector”
Further inspection of 4 also shows unusually long Al(1) Cl(1) and Al(2) Cl(2) bond
distances, 2.354(2) and 2.3939(19) Å, respectively, which are substantially longer than average
Al Cl bond lengths (2.15 Å av.) previously reported for other m-terphenylaluminum chloride
compounds.120,121 These bond distances are surprisingly more comparable to the Al Br bond
distances in [RAlBr3Li]2 (R = 2,6-Mes2C6H3) (2.285(6), 2.359(5), and 2.398(5) Å)119 and even
longer than those in either RAlBr2·OEt2 (R = 2,4,6-Ph3C6H2-) (2.297(3) and 2.302(3) Å)118 or 3
(2.3175(17) Å and 2.3010(16) Å). For comparison purposes, the Al(1) O(1) and Al(2) O(1)
bond distances (1.696(4) and 1.691(4) Å) are substantially shorter than the bridging Al OH Al
bond distances (1.817(2) Å) in [RAlCl(μ-OH)]2 (R =2,6-(2,4,6-i-Pr3C6H2)2C6H3-), yet the two
aluminum atoms are well separated (Al Al = 3.335Å).
These odd structural anomalies of 4 may be partially attributed to the anomeric effect.
Evidence for this proposal may be supported with previous studies in carbohydrate chemistry,
where the anomeric effect has long been used to describe why -substituents to the oxygen atom
in pyranose rings prefer the axial position, regardless of 1,3 diaxial steric congestion.122
Furthermore, in acyclic systems such as -halomethyl ethers, MeOCH2X, the anomeric effect
has been used to explain why the gauche conformation is more stable than trans, their C X bond
distances are elongated, and the C O bond distance is shortened.123 All of these features are
found in 4. Although the exact cause of the anomeric effect is debatable, it is generally accepted
Cl
R OEt2
Al
Cl
OEt2R
52
that a stabilizing interaction occurs by hyperconjugation in which the lone pair of electrons of the
less electronegative element donates into the *-orbital of the C X bond. The “no bond/double
bond” resonance model (Figure 2.7) paints a clearer picture. In effect, this theory results in two
resonance forms at equilibrium the base molecule and hypothetical H2C=OMe+ intermediate,
with release of a halide ion.
MeO CH2 X MeO CH2 X
Figure 2.7. “Double bond-no bond” resonance model for -halomethyl ethers
With the longer than expected Al Cl bond lengths, short Al O bond lengths, and the
“gauche-type” orientation of the m-terphenyl ligands in compound 4, it is, indeed, compelling to
suggest that the anomeric effect is influencing these structural manifestations. Furthermore, as
shown in Figure 2.8, the “double-bond/no-bond” resonance model can be applied to 4. Since the
two resonance forms are averaged in the solid state, this may account for the long Al Cl and
short Al O bonds distances in 4. The gauche-like configuration of the m-terphenyl ligands may
also be attributed to the anomeric effect, wherein the molecule assumes a conformation that is
optimal for the lone pair of electrons on oxygen to align with a chloride ligand, even at the
expense of steric interactions between the ligands. Another notable feature of 4 is the almost
linear Al(1)-O(1)-Al(2) bond angle (160.0(2)°), which is over 55° larger than the corresponding
H O H bond angle (104.5°) calculated for H2O.124 Clearly, the bulky ligands in 4 have some
responsibility for this structural observation, yet one could question if the anomeric effect is
influencing this bond angle as well.
53
OAl
R
Cl
OAl
R
Cl
Figure 2.8 The “double bond-no bond” resonance model for 4.
Consideration of the X-ray structure of 5, R3In, (Fig. 2.9), which crystallizes as a
monomer with one molecule of diethyl ether per asymmetric unit, reveals the first tris-m-
terphenylindium and provides an interesting contrast from the organogroup 13 halides discussed
above. The three ligands in 5 are arranged about the indium atom in a propeller like fashion and
are not crystallographically equivalent due to differing dihedral angles. The dihedral planes were
found to be 39.84°, 31.95°, and 65.37° for the C(1), C(27) and C(53) with respect to the central
phenyl ring planes, respectively. Indeed, it is remarkable that three sterically imposing ligand are
able to arrange in an orientation that is conducive for formation of 5. It is clear that the lack of
substituents at the ortho-positions of outer phenyl rings affords conformational freedom that
would otherwise be hindered with substitution. The indium atom in 5 resides in a distorted
trigonal planar coordination environment, demonstrated by its differing C–In–C angles: C(1)–
In(1)–C(27) 114.77(13)°, C(1)–In(1)–C(53) 120.34(12)°, C(27)–In(1)–C(53), 124.83(13)°.
Indeed, these bond angles are comparable with those trimesitylindium, Mes3In,125 and
triphenylindium, Ph3In.36,38 However, when these angles are compared with the C In C bond
angle (157.3(8)°) in the more bulky and somewhat related bis(m-terphenyl)indium bromide, 2,6-
Mes2C6H3InBr,126 they are clearly smaller. The In–C bonds in 5 (In(1)–C(1) 2.200(3) Å, In(1)–
C(27) 2.199(3) Å, In(1)–C(53) 2.193(3) Å) are longer to those in Mes3In (2.170(5) Å; 2.170(5)
Å; 2.163(5) Å) and 2,6-Mes2C6H3InBr (2.171(25) and 2.166(26) Å), and more so for those in
Ph3In (2.111(14) Å and 2.155(14) Å).
54
Figure 2.9. Molecular structure of R3In (5)
Table 2.5 Selected bond distances [Å] and angles [°] for R3In (5)
Atoms Distance Atoms Angle In(1) C(53) 2.192(3) C(53) In(1) C(1) 120.29(13) In(1) C(1) 2.199(3) C(53) In(1) C(27) 124.86(13) In(1) C(27) 2.200(3) C(1) In(1) C(27) 114.79(13)
55
2.1.4 Synthesis and Structures of 2,6-Di(4-methylpheny)phenyl Group 13 Complexes
As to augment our studies of less sterically demanding m-terphenyl ligands on group 13
metals, we selected 2,6-(4-Me-C6H4)2C6H3- (R ) to ascertain if differences in para-substituents,
methyl as opposed to tert-butyl, on the outer phenyl rings play a significant role in the stability
and structural properties of the respective ligand–metal complexes. Reactions of R Li were
conducted with GaCl3 and InCl3 (Eq. 2.3). In general, crystallizing the corresponding ligand–
group 13 complexes proved more difficult than complexes 1-5 due to a persistent oily residue
that leached from solution. However, after considerable effort, X-ray quality crystals were
isolated for three new compounds: [R GaCl3][Li(OEt2)2] (6), [R InCl3][Li(OEt2)(THF)] (7), and
R 3In (8). These compounds tended to have lower thermal stabilities when compared to the
analogous compounds 1-5. Moreover, compounds 6 and 7 decomposed on melting and are air-
and moisture-sensitive, while 8 shows no signs of decomposition when exposed to air. These
compounds were characterized by single crystal X-ray crystallography, 1H NMR, elemental
analysis, and melting point determination.
Reaction of R Li with GaCl3 in diethyl ether (Eq. 2.3) proceeds smoothly to afford
colorless X-ray quality crystals of 6 [R GaCl3][Li(OEt2)2] from viscous brown oil. However,
allowing R Li to react with InCl3 gave two considerably different products depending on solvent
employed (Eq. 2.3). To much surprise, when the reaction is carried out in neat diethyl ether a
tris-(m-terphenyl)indium, R 3In (8), is isolated as colorless crystals, however when performed in
mixed solvent (diethyl ether/THF, 10:1) a monomeric anionic m-terphenyl indium trichloride,
[R InCl3][Li(OEt2)(THF)] (7), is produced. The preponderance for the formation of either
compound may be traced to the solubility of InCl3. Because InCl3 is only sparingly soluble in
diethyl ether, it is easy to consider that R Li reacts multiply with only solubilized InCl3 resulting
56
in the isolation of 8. Conversely, InCl3 is readily soluble in THF at room temperature and the
reaction proceeds as stoichiometrically dictated to give 7. This observation lends rationale to the
formation of the tris-(m-terphenyl)indium, R3In (5), which was also generated in diethyl ether.
R 3In
8
[R InCl3][Li(Et2O)(THF)]R = R Li
InCl3, Et2O -78°C
- 3 LiCl
GaCl3, Et2O -78°C
InCl3, THF/Et2O, r.t.
[R GaCl3][Li(OEt2)2]
6
7
(2.3)
The X-ray structure of [R GaCl3][Li(OEt2)2] (6) (Fig. 2.10) provides an opportunity to
compare its structure with compound 1, RGaCl2(OEt2), which has t-butyl functionality at para-
position of the m-terphenyl ligand. The most striking distinction between these two four-
coordinate organogallium halides is in which the manner the tetrahedral geometries about the
gallium atoms are obtained. While 1 is a neutral m-terphenylgallium halide, 6 is anionic with
three chloride ligands surrounding gallium, coupled with a lithium cation. It should be noted that
the syntheses of 1 and 6 were performed following identical protocols; therefore the structural
deviations may be possibly attributed to the electronic effects of the m-terphenyl ligands. This
may be an oversimplification of the exact cause of the different adduct formations, however it is
well known that methyl groups are weaker -electron donors than t-butyl groups, due to
enhanced hyperconjugation in the latter. This would undoubtedly affect the Lewis acidity of the
57
gallium atoms and thus the preference for either anionic, RGaCl3Li, or diethyl ether,
RGaCl2(OEt2), adduct formation. The different coordination spheres of the gallium atoms appear
to have only a modest affect on the Ga C bond distances in 1 and 6 (1.98(5) Å and 1.970(4) Å,
respectively), as both are quite similar. The Ga(1) C(1) bond distance in 6 also compares well
with those of previously reported four-coordinate m-terphenylgallium halides (1.930(8) to
1.985(1) Å).44,46,117 A review of the literature reveals that m-terphenylgallium dihalides are
commonly reported as dimers [RGaCl2]2 and that anionic species are fairly rare but usually
feature m-terphenyl ligands that are devoid of ortho-substitution on the flanking phenyl rings,
2,4,6-Ph3PhGaCl3 and 2,6-Ph2PhGaCl3.44 This provides further evidence that the steric and
electronic effects of the m-terphenyl ligands has an immense effect on structure and bonding in
group 13 chemistry. Indeed, the structure of 6 is consistent with 2,4,6-Ph3PhGaCl3 and 2,6-
Ph2PhGaCl3, all comprising of three chlorine atoms surrounding the gallium atom. Two of the
chlorine atoms in 6 are coordinated with lithium to form a slightly puckered Ga(μ-Cl2)Li four-
membered ring, which contains bond angles that are all slightly less than 90° except for the
Cl(1)-Ga(1)-Cl(2) bond angle (95.25(5)°). The Ga(1)–Cl(1) and Ga(1)–Cl(2) bond distances
(2.2503(14) and 2.2530(13) Å, respectively), which are incorporated in the Ga(μ-Cl2)Li four-
membered ring, are longer than the terminal Ga(1)–Cl(3) bond distance (2.2759(13) Å). This is
consistent with the extremely sterically encumbered m-terphenyl gallium dichloride dimer,
[RGaCl2]2 (R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-2), which also has longer terminal Ga Cl bond
distances (2.196-2.201 Å) than bridging ones (2.230Å). On average, the Ga Cl bonds compare
with those in 2,4,6-Ph3PhGaCl3 and 2,6-Ph2PhGaCl3 (2.239 Å av) but are slightly longer than
those in 1 (2.205(2) and 2.1872(13) Å); however, the Li Cl bond distances in 2,4,6-Ph3PhGaCl3
and 2,6-Ph2PhGaCl3 were not reported, thus it is difficult to place those of 6 into perspective.
58
Figure 2.10. Molecular structure of [R GaCl3][Li(OEt2)2] (6)
Table 2.6 Selected bond distances [Å] and angles [°] for [R GaCl3][Li(OEt2)2] (6)
Atoms Distance Atoms Angle Ga(1) C(1) 1.970(4) C(1) Ga(1) Cl(1) 113.22(13) Ga(1) Cl(1) 2.2503(14) C(1) Ga(1) Cl(2) 109.80(13) Ga(1) Cl(2) 2.2530(13) Cl(1) Ga(1) Cl(2) 95.25(5) Ga(1) Cl(3) 2.2759(13) C(1) Ga(1) Cl(3) 122.49(13) Cl(1) Li(1) 2.406(10) Cl(1) Ga(1) Cl(3) 105.56(6)
Cl(2) Li(1) 2.397(10) Cl(2) Ga(1) Cl(3) 106.97(6)
59
Moving on, the single crystal X-ray structure of 7, [R InCl3][Li(OEt2)(THF)]) (Fig. 2.
11), reveals the first m-terphenyl indium trihalide lithium adduct. In fact, there has been only
one other account of an m-terphenyl-indium dihalide, [RInCl2]2 (R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-
), in the literature, which was reported by two independent groups.115,117 Compound 7 is
isoelectronic with [R GaCl3][Li(OEt2)2] (6); however, it has coordination of both a molecule of
diethyl ether and THF about the lithium cation. Though both solvents were used in the synthesis
of 7, it is peculiar that the more polar THF molecule did not displace diethyl ether. The indium
atom in 7 resides in a distorted tetrahedral environment surrounded by three chloride ligands and
the m-terphenyl ligand. Similar to that in 6, two of the chloride ligands in 7 have lithium
interactions to form a puckered Li(μ-Cl2)In four-membered ring. The Li(1) Cl(1) and Li(1)-
Cl(2) bond distances (2.34(3) and 2.50(3) Å, respectively), which are incorporated in the ring,
differ by almost 0.2 Å. However, it appears that the differences between these bond distances
have a modest effect on Li(1) Cl(1) In(1) and Li(1) Cl(2) In(1) bond angles, 89.1(6)° and
85.6(6)°, respectively. The In(1) Cl(1) and In(1) Cl(2) bond distances (2.442(4) Å and 2.438(4)
Å, respectively) in 7 are almost identical, but both bond distances are slightly longer than the
terminal In(1) Cl(3) bond distance (2.398(4) Å). This structural feature is contrary to that found
for 6, wherein the terminal Ga Cl bond is longer than those with Cl Li interactions.
Furthermore, the differences (0.05 Å av) between the terminal In Cl bond distance and the two
engaged with Li interactions are comparably larger that the analogous differences for Ga Cl
bonds distances of 6 (0.025 Å av). Perhaps the larger atomic radius of indium allows for stronger
interaction of the terminal chloride ligand. The In(1)–C(1) bond distance (2.133(13) Å) in 7 is
relatively smaller than those in the tris-m-terphenylindium compound 5 (R3In, (2.1868(17)-
2.2043(16) Å), which is undoubtedly due to steric repulsion of the three bulky ligands. It is also
60
prudent to compare some structural features of 7 with the only other m-terphenyl-indium halide
dimer, [RInCl2]2 (R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-).115,117 The In(1) C(1) bond distance
(2.133(13) Å) in 7 is shorter than (2.1485(3) Å) that of [RInCl2]2, while the In Cl bond distances
in 7 (2.398(4)term, 2.442(4)bridge, and 2.438(4)bridge Å) are all longer than the terminal In Cl bond
distance (2.3341(12) Å) but substantially shorter than the bridging In Cl bond distances
(2.5239(7) Å) in [RInCl2]2.
The single crystal X-ray structure of 8 (Fig. 2.12) reveals another tris-m-terphenylindium
with the three ligands essentially encapsulating the pseudo-trigonal planar indium atom. This is
clearly demonstrated with the space-filling model of 8 (Fig. 2.13). Compound 8 is structurally
very similar to R3In (5). Interestingly, although 5 contains m-terphenyl ligands with more bulky
t-butyl groups, the ligands are arranged about the indium atom in a fairly symmetrical fashion
with similar C In C bond angles. This is not the case for 8, as the C(1)–In(1)–C(41) and C(21)–
In(1)–C(41) bond angles, 123.80(6)° and 123.52(6)°, respectively, are significantly larger than
the complementary C(1)–In(1)–C(21) bond angle (112.66(6)°), resulting in a less symmetrical
coordination sphere around indium. The In(1)–C(1) and In(1)–C(21) bonds distances (2.2043(16)
and 2.2019(16) Å, respectively) compare well with those in 5 ((In(1)–C(1) 2.200(3) Å, In(1)–
C(27) 2.199(3) Å, In(1)–C(53) 2.193(3) Å), however the In(1)–C(41) bond (2.1868(17) Å) in 8
is somewhat shorter. The reason for this variation is not clear. A comparison of the In–C bonds
in 8 with other triarylindium complexes indicate that they are slightly longer than those of Ph3In
(2.111(14)-2.155(14) Å),37 and trimesitylindium Mes3In, (2.163(5)-2.170(5) Å).125 This may
reflect the added steric encumbrance of 8.
61
Figure 2.11. Molecular structure of [R InCl3][Li(OEt2)(THF)] (7)
Table 2.7 Selected bond distances [Å] and angles [°] for [R InCl3] [Li(OEt2)(THF)] (7)
Atoms Distance Atoms Angle In(1) C(1) 2.133(13) C(1) In(1) Cl(3) 121.2(4) In(1) Cl(3) 2.398(4) C(1) In(1) Cl(2) 115.3(4) In(1) Cl(2) 2.438(4) Cl(3) In(1) Cl(2) 104.74(16) In(1) Cl(1) 2.442(4) C(1) In(1) Cl(1) 115.7(4) Cl(1) Li(1) 2.34(3) Cl(3) In(1) Cl(1) 104.00(14) Cl(2) Li(1) 2.50(3) Cl(2) In(1) Cl(1) 91.33(14)
62
Figure 2.12. Molecular Structure of R 3In (8)
Table 2.8 Selected bond distances [Å] and angles [°] for R 3In (8)
Atoms Distance Atoms Angle
In(1) C(41) 2.1868(17) C(41) In(1) C(21) 123.52(6)
In(1) C(21) 2.2019(16) C(41) In(1) C(1) 123.80(6)
In(1) C(1) 2.2043(16) C(21) In(1) C(1) 112.66(6)
63
Figure 2.13. Space filling model of R 3In (8)
In summary, reaction of RLi and R Li with group 13 salts provides a number of
structurally interesting organometallic group 13 complexes. Specifically, reaction with RLi with
GaCl3 in a 1:1 ratio led to the formation of an m-terphenyl gallium dichloride etherate,
RGaCl3(OET2) (1), while an m-terphenyl gallium trichloride lithium adduct
[R GaCl3][Li(OEt2)2] (6) was isolated by reaction of R Li under identical reaction conditions.
Moreover, the isolations of RAlBr2(OEt2) (3) and [R InCl3][Li(OEt2)(THF)] (7) suggest that the
different adduct formations, diethyl coordination or anionic group 13 lithium salts, may be a
trend decidedly influenced by the electron donating effects of para-substituents. Overall, the
structure and bonding of ligands R and R on the group 13 metals were very similar to previously
synthesized m-terphenyl group 13 halides; however, some notable complexes had novel
structures. In particular, compound 4 with its gauche-type conformation of the m-terphenyl
ligands, exceeding long Al Cl bond distances, and short Al O bond distances are conspicuous
characteristics of the anomeric effect, which is rarely found in group 13 chemistry. Also R3In (5)
and R 3In (8) are notable as the first tris-m-terphenyl group 13 compounds. The lack of ortho-
64
substituents on the flanking phenyl rings affords conformation freedom so that three of these
relatively bulky ligands are well accommodated about the indium atom.
2.1.5 Synthesis and Molecular Structure of [R3Ga3][Na3 (OEt2)3] (9) (R = 2,6-(4-t-BuC6H4)2C6H3-)
Alkali metal reductions of m-terphenyl group 13 halides, REX2, have been a fruitful
means to synthesize organometallic group 13 compounds containing metal metal bonds. Our
previous endeavors have shown that metal contact aggregation increases with decreasing ligand
steric bulk. For example, when 2,6-Mes2C6H3GaCl2 is reduced with sodium or potassium metal
tri-gallium complexes comprising of a Ga3-cyclic ring, M2[GaR]3 (M = Na,127 K;25 R = 2,6-
Mes2C6H3-, Mes = 2,4,6-Me3C6H2-) (cyclotrigallenes), are isolated, while on the other hand,
reduction of the more sterically encumbered 2,6-(2,4,6-i-Pr3C6H2)2C6H3GaCl2 yields a di-gallium
complex Na2[RGa GaR] (R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-) (digallyne) (Fig. 1.13) containing a
Ga Ga triple bond.21 It was hypothesized that by alkali metal reductions of the less bulky m-
terphenyl group 13 halides, REX2(OEt2) and [R EX3][Li(OEt2)2], metallic clusters or cyclic
compounds with higher metal metal bonding aggregation could be stabilized. Unfortunately the
results of these endeavors were less than desirable, usually resulting in the isolations of only
ligand hydrocarbons, RH, as a result of C E bond cleavage (E = Al, Ga, In). In only one
experiment was a compound containing E E bonds isolated, wherein sodium metal reduction of
RGaCl2(OEt2) (1) (R = 2,6-(4-t-BuC6H4)2C6H3-) in diethyl ether provides orange-red crystals of
9, [R3Ga][Na3(OEt2)3] (Eq. 2.4). Unfortunately, due to low yield complete characterization
proved impossible, however a few crystals were adequate for single crystal X-ray
crystallography.
65
R
t-Bu
Ga
Ga Ga
R
R
t-But-Bu
H
H
[Na3(OEt2)3]
R = 4-t-BuC6H4-
9
RGaCl2(OEt2)Na/Et2O
1
Single crystal X-ray analysis of 9 (Fig. 2.14) reveals a complex containing a chain of
three gallium atoms with each forming a GaC4 five-membered ring with the m-terphenyl ligand.
Though catenation is common for the group 14 elements, it is rare for the group 13 elements.
Indeed, there are only two reports of open-chain catenated group 13 species,128,129 and only one
gallium species, [I2(PEt3)GaGaI(PEt3)Ga(PEt3)I].129 The formation of 9 is not well understood,
however it appears that the ortho-positions of the outer phenyl are activated to form the three
GaC4 five-membered rings. This unusual phenomenon was also observed for Wehmschulte130,131
and coworkers, whereby reaction of RLi (R = 2,6-(4-t-BuC6H4)2C6H3-) with H2ClB•SMe2 at -
78°C yields unsymmetrical 9-borafluorenes via facile intramolecular C–H bond activation of the
flanking phenyl rings. Moreover, the presence of the three sodium atoms suggests that 9 is a
trianionic complex, even though only the central four-coordinated gallium warrants a –1 formal
charge. The most feasible explanation for this occurrence could be the existence of hydrides
residing on the pyramidal three-coordinate Ga(2) and Ga(3) atoms. Although the hydrides were
not absolutely located, this would fully account for the trianionic nature of 9.
(2.4)
66
Figure 2.14. Molecular structure of [R3Ga3][Na3(OEt2)3] (9)
Table 2.9 Selected bond distances [Å] and angles [°] for [R3Ga3][Na3(OEt2)3] (9)
Atoms Distance Atoms Angle
Ga(1) Ga(2) 2.4863(10) Ga(2) Ga(1) Ga(3) 107.79(3)
Ga(1) Ga(3) 2.5251(10) C(8) Ga(1) C(1) 84.9(3)
67
A number of structural features of 9 merit discussion. Particularly, the Ga C bond
distances (2.039 Å av) are significantly longer than that in the starting material RGaCl2•(OEt2)
(1) (1.985(5) Å) and also those in the previously reported gallium five-membered heterocycle
[(PhC=CPh)2GaCl2][Li(OEt2)]2 (1.966(4)Å),132 and the spirogallane{[(PhC=CPh)2]2Ga}- (2.012
Å av).133 The lengthening of the Ga C bonds in 9 may likely be the result of angle strain induced
by bonding with the outer phenyl rings. To place this hypothesis in further perspective, the two
C C C bond angles (117° av) incorporated in the GaC4 five-membered ring are much more
acute than the analogous bond angle involving the ipso-carbons on the central phenyl ring to
“free” flanking phenyl ring (C C C <120° av). Moreover, angle strain is also exhibited by the
Ga C bonds, which are slightly “bent” (166° av) from linearity with respect to the para-carbon
of the central phenyl ring. The ramification of this angle strain is a weakened Ga C bond. The
three GaC4 five-membered rings in 9 are essential planar and have an average C–Ga–C bond
angle of 85°, which consistent with previously published five-membered gallium carbocycles
(galloles).132,134-137 The Ga Ga bond distances in 9 are also interesting, as the Ga(1)–Ga(2) bond
distance (2.4863(10) Å) is slightly longer than the Ga(2)–Ga(3) bond distance (2.5251(10) Å).
The terminal Ga(2) and Ga(3) atoms in 9 are well separated (4.049Å) as to preclude Ga Ga bond
formation. A comparison of 9 with the only other catenated gallium species,
[I2(PEt3)GaGaI(PEt3)Ga(PEt3)I2]129 is revealing. The Ga Ga bond distances in 9 (2.4863(10) and
2.5251(10) Å) are longer and the Ga(1)–Ga(2)–Ga(3) bond angle (107.79(3)°) is smaller than the
respective structural factors in [I2(PEt3)GaGaI(PEt3)Ga(PEt3)I2] (2.451(1) and 2.460(1) Å;
121.9(1)°). The smaller Ga Ga Ga in 9 may be attributed to two factors: a) the less bulky
triethyl phosphine ligands in [I2(PEt3)GaGaI(PEt3)Ga(PEt3)I2], which has a cone angle that
protrudes away from the metal centers, allowing for angular freedom; or b) intramolecular
68
coordination of the Na atoms with the m-terphenyl ligands in 9 contracts the Ga Ga Ga bond
angle. The three sodium atoms of 9 are also interesting as each has an explicitly different
coordination environment. The eight-coordinate Na(1) atom is complexed with two phenyl rings
of opposing m-terphenyl ligands one in 6-fashion and the other 2, while the Na(2) atom is
three-coordinate, afforded by interactions with the flanking and central phenyl rings of different
m-terphenyl ligands and a molecule of diethyl ether. The Na(3) atom is four-coordinate and has
only one interaction with the m-terphenyl ligand (C Na(3) = 2.644Å) and a slight interaction
with the Ga(2) atoms (Na(3) Ga(2) = 2.978Å). Its coordination sphere is rounded out with two
diethyl ether molecules.
To conclude, alkali metal reductions of less bulky m-terphenyl group 13 halides,
REX2(OEt2) and [R EX2][Li(OEt2)2] were generally unsuccessful at producing compounds with
metal metal bonds. Perhaps the ligands are too small to adequately shield the metal centers. This
process may be further complicated by C H activation of the unsubstituted ortho- position of the
outer phenyl rings, which was possibly the case in 9. Thus, substitution at this position appears to
have a secondary purpose besides steric protection in low-valent, low-coordinate
organometallic group 13 chemistry, that is, to avoid hydride formation.
2.2 Organometallic Group 13-Group 4 Complexes
2.2.1 Synthesis and Structures of Cp2Hf(ER)2 Compounds (10 E = Ga; 11 E = In; R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-)
Typically the Robinson group has had limited excursions into the organometallic
chemistry of transition metals. However, given the considerable number of homogeneous
Ziegler-Natta olefin polymerization catalytic systems involving the early metallocene dihalide
69
derivatives, Cp2MX2 (Cp = C5H5; M = Ti, Zr, Hf),138 and organo-group 13 metal moieties, it was
surprising that examples of compounds containing directly bound group 4 group 13 metals
were unknown. Thus, we became interested in synthesizing such organometallic compounds not
only because the nature of the transition metal main group metal bond is intriguing, but also for
the possibility of catalytic function.84,139-145 In 2004, we reported a series of Cp2M(ER)2
compounds (M = Ti, Zr; E = Ga, In; R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-) containing the first group
4 group 13 bonds with interesting “V shaped” E M E architectures.146,147 As a natural
progression in the development of this burgeoning sector of organometallic chemistry, the
synthesis of compounds possessing group 13–Hf bonds was pursued.
Employing our generalized strategy of stabilizing low-valent, low-coordinate main group
species with sterically demanding ligands, Cp2Hf(GaR)2 (10) and Cp2Hf(InR)2 (11) were
prepared by sodium metal reduction of REX2 (E = Ga, In; R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-) and
Cp2HfCl2 in diethyl ether (Eq. 2.5). Compounds 10 and 11 are isolated as dark-green and dark-
purple crystals, respectively. Surprisingly, though both 10 and 11 are extremely sensitive to air
and moisture, they exhibit exceptionally high thermal stability, melting or decomposing above
270°C. Moreover, these compounds are noteworthy as the only examples with unsupported
Hf group 13 bonds and join the small collection of compounds containing group 4–group 13
bonds.146-149
RECl2 HfCl
Cl 6 Na
- 6NaClHf
E
E
R
R
+
R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-E = Ga (10), In (11)
2
(2.5)
70
The metamorphosis of the formal oxidation states of the metals from starting materials to
compounds 10 and 11 is fascinating. The group 13 metals in REX2 are formally reduced from EIII
to E1, while the HfIV atom in Cp2HfCl2 is converted to HfII, transforming the formerly 16-
electron hafnocene dichloride, Cp2HfCl2, into 18-electron Cp2Hf(ER)2 complexes. The two
linear RE: fragments in 10 and 11 seem to behave as two-electron donors and are reminiscent of
:CO in hafnocene dicarbonyl, Cp2Hf(CO)2.150
Indeed, group 13 diyls, RE:, have considerable Lewis basic and -donor properties and
are well known for their ability to mimic N-heterocyclic carbenes. Moreover, the group 13 diyls
can effectively stabilize transition metals in low oxidations states by forming donor-acceptor
complexes which has provided a viable means to synthesize an array of new compounds and
complexes containing group 13 metal transition metal bonds.151-157 More recently compounds
containing group 13 lanthanide bonds (Ga Nd,158 Al Eu, and Al Yb159) have also been
obtained by utilizing this strategy. While group 13 diyls are commonly stabilized by Cp* (Cp* =
C5Me5)160 or -diketiminate ligands ({(Ar)N(Me)C}CH-),149 the X-ray structures of m-
terphenylindium and thallium diyls (2,6-(2,4,6-i-Pr3C6H2)2C6H3E:, E = In47, Tl161) have been
isolated and confirms the ability m-terphenyl ligands to stabilize group 13 diyls. Furthermore,
although X-ray crystallographic analysis does not exist, spectroscopic and chemical evidence
supports the existence an m-terphenylgallium diyl, RGa: (R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-).162
Thus, it is not far fetched to consider that the “RE” fragments in 10 and 11 are indeed acting as
two electron donors to the Hf center.
71
Single crystal X-ray analysis was performed to provide further insight into the structure
and bonding of 10 and 11. Although crystals of 10 and 11 differ dramatically in color, dark green
and purple, respectively, their crystal structures are both isostructural and isomorphous. Both
crystallize in the orthorhombic (Pbcn) space group with a single molecule of diethyl ether in the
asymmetric unit.
The crystal structures of 10 (Fig. 2.15) and 11 (Fig. 2.16) reveal trimetallic Cp2Hf(ER2)
(10, E = Ga, 11, E = In) complexes with the two RE: fragments coordinated to a central
tetrahedral hafnocene moiety “HfCp2” in a “V-shape” E–Hf–E bonding motif. The E–Hf–E bond
angles in 10 and 11 of 100.76(6)° and 95.26(4)°, respectively, compare well with the
corresponding E–M–E bond angles (97° av.) in the isoelectronic Cp2M(ER)2 (M = Ti, Zr; E =
Ga, In) complexes. The two-coordinate group 13 metals form an essentially linear Hf E C bond
angle (Hf(1)-Ga(1) C(1) = 171.7(3)°; Hf(1)-In(1) C(1) = 171°) with the ligand and hafnium
metal. The slight deviation from linearity is undoubtedly due to steric repulsion between the
bulky ligands. The most dominant structural feature of 10 and 11 is the m-terphenyl ligands. The
Hf–E bonds, however, are the most notable feature of these compounds. It is difficult to assess
the Hf–E bond distances in 10 and 11 (Hf(1)–Ga(1) = 2.6198(13) Å; Hf(1)–In(1) = 2.7667(10)
Å) due to the absence of examples with which compare, though they are substantially shorter
than the sum of their respective covalent radii (Hf–Ga = 2.76 Å; Hf(1)–In(1) = 2.94 Å). The
possibility for E E bonding in 10 and 11 is eliminated due to exceedingly long Ga Ga and
In In contacts (4.036 Å and 4.088 Å, respectively), which are well out of range for metal metal
bonding (sum of covalent radii, Ga = 2.52; In = 2.88 ).
72
Figure 2.15. Molecular structure of Cp2Hf(GaR)2 (10)
Table 2.10 Selected bond distances [Å] and angles [°] for Cp2Hf(GaR)2 (10)
Atoms Distance Atoms Angle Hf(1) Ga(1) 2.6198(13) Ga(1) Hf(1) Ga(1A) 100.76(6) Ga(1) C(1) 2.021(10) C(1) Ga(1) Hf(1) 171.7(3)
73
Figure 2.16. Molecular structure of Cp2Hf(InR)2 (11)
Table 2.11 Selected bond distances [Å] and angles [°] for Cp2Hf(GaR)2 (11)
Atoms Distance Atoms Angle Hf(1) In(1) 2.7667(10) In(1) Hf(1) In(1A) 95.26(4) In(1) C(1) 2.194(13) C(1) In(1) Hf(1) 171.3(3)
74
For more detailed discussion of the bonding of 10 and 11, our previous DFT calculations
on Cp2M(EPh)2 (M = Zr, E= Ga) provide evidence to suggest that the relatively short M–E bonds
are a result of a donor–acceptor M E -bond that is augmented by M E -back-bonding.147
Furthermore, these computations revealed detailed molecular orbital descriptions (Fig. 2.17) that
show the M E bonds are a culmination of the antisymmetric HOMO-1 and symmetric HOMO-2
orbitals, wherein the sp-orbitals of the main group metals donate electrons into the empty d-
orbitals of the group 4 metal, and the HOMO is indicative of -back-bonding from the Cp2M
fragment into the essentially linear RE: fragment. A similar conclusion was discerned
computationally for two similar compounds, RInMnCp(CO)2140 and RGaFe(CO)4,
163 which also
suggested the short E M bonds were the result of substantial M E -back-bonding.164
Figure 2. 17. DFT calculated HOMO, HOMO-1 and HOM-2 orbital for Cp2M(ER)2 compounds
2.2.2 Synthesis and Structure of (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12)
It is well known that ligand steric properties can influence metal aggregation in
compounds containing homonuclear main group metal metal bonds. In this same regard, we
pondered how does this factor affect the structure and bonding of organometallic species
containing group 13 group 4 bonds. We have previously shown that when RBiCl2 (R = 2,6-
Mes2C6H3-) and Cp2ZrCl2 are reduced with sodium metal, a Cp2Zr(BiR)2 complex containing a
75
ZrBi2 trimetallic ring is formed.165 This is contrary to the “V shaped” E M E metallic cores
observed in the Cp2Hf(ER)2 compounds 10 and 11. Indeed, this inspired us to gain further insight
into the effect of utilizing even smaller ligands to stabilize group 13 group 4 bonds. Fortunately,
our studies of m-terphenyl ligands, 2,6-(4-t-BuC6H4)2C6H3- (R) and 2,6-(4-Me-C6H4)2C6H3- (R ),
on group 13 metal halides provided adequate precursors to examine in these endeavors.
Though several experiments were performed with various group 13 metals, group 4
metallocenes, ligands, and solvents, only one of these reactions gave crystals adequate for single
crystal X-ray analysis. In particular, the sodium metal reduction of RGaCl2·OEt2 (1) in the
presence of Cp2ZrCl2 was performed, wherein the initial colorless solution transforms from
green to almost black over several days (Eq. 2.6). After “hot” filtration of the mother solution
and placing the solution at room temperature for several days, rectangular dark purple crystals
were isolated (12 %).
(C10H8)(ZrCp)2(μ H)(μ Cl)(μ-GaR)RGaCl2(Et2O) + Cp2ZrCl2Na/ Et2O
1 12 (2.6)
Upon single crystal X-ray structural analysis a trimetallic fulvalene-bridged
dizirconocene-gallium complex containing Ga Zr bonds was revealed, 12 (Fig. 2.18).
Compound 12 is notable as the first example of gallium bonded with two zirconium atoms. The
literature reveals only two somewhat related aluminum-based compounds containing bridging
hydride ligands: (C10H8)[CpTi]2(μ-H)(H2AlEt2),166 and [Cp2Zr(μ-H)]2(μ-H)AlCl2.
167 In
accordance with standard electron counting of the structure 12, the zirconium atoms would be of
mixed oxidation states (+3 and +4). This would provide a compound with paramagnetic
76
properties, however 12 is ESR silent. Furthermore, radicals commonly distort 1H NMR spectra
by paramagnetic line broadening, but the spectrum of 12 correlates well with its X-ray structure
except for a singlet signal at -4.316 ppm. Initially, this signal was attributed to signal noise or
contaminates; however, after rigorous purification and varying the deuterated solvents, the signal
remained. Moreover, this 1H NMR signal (-4.316 ppm) in 12 compares well with the analogous
bridging dizirconium hydride, Zr H Zr, signal (-4.67ppm) in the cationic dizirconium complex
[(C10H8)Zr2(μ-Cl)(μ-H)(CH2C CSiMe3)][BMe(C6F5)3], and there are no signals in the spectrum
to suggest a terminal Zr H hydride (3.03 to 7.25 ppm).168-171 It was anticipated that a hydrogen
atom that was undetected by X-ray crystallography techniques might be present in the structure
of 12.
The literature provides two reports that are related to 12 for possible clues to hydride
sources. Indeed, it has been reported that the sodium amalgam reduction of Cp2ZrCl2 forms a
fulvalene bridged dizirconocene complex, (C10H8)[CpZr(μ-Cl)]2, by means of cyclopentadienyl
ligand C–H activation172 and that unsymmetrical 9-borafluorenes are formed by a facile
intramolecular C–H activation of the identical m-terphenyl ligand used in 12.130,131 Both of these
processes generate putative hydride formation.
77
Figure 2.18. Molecular structure of (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12)
Table 2.12 Selected bond distances [Å] and angles [°] for (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12)
Atoms Distance Atoms Angle Ga(1) C(1) 2.019(5) Zr(1) Ga(1) Zr(2) 77.33(2) Ga(1) Zr(1) 2.7457(9) Cl(1) Zr(2) Ga(1) 92.76(4) Ga(1) Zr(2) 2.8796(10) Zr(1) Cl(1) Zr(2) 84.73(4) Zr(1) Cl(1) 2.6033(13) Cl(1) Zr(1) Ga(1) 96.17(4) Zr(2) Cl(1) 2.6141(13) Cl(1) Zr(2) Ga(1) 92.76(4)
78
To ascertain where a possible Zr H Zr hydride signal in 12 should appear in its 1H NMR
spectrum, a theoretical spectrum of a model compound, 12a (C10H8)[CpZr]2(μ-H)(μ-Cl)(μ-GaR)
(R = 2,6-Me2C6H3-) (Fig. 2.19), was computed at the GIAO-PW91PW91/LANL2DZ/-
/PW91/LANL2DZ level. The theoretical chemical shift of the bridging hydride signal (-5.00
ppm) in 12a is comparable to that observed for the experimental value in 12 (-4.316 ppm). The
deviation in chemical shifts may be attributed to the differing chemical environments, primarily
due to the anisotropic effects of the bulky m-terphenyl ligand. In an effort to better understand
the nature of the hydride, density functional theory (DFT) computations were performed on 12a.
Two different methods, B3LYP and PW91PW91, were used in conjunction with the LANL2DZ
basis set for the optimization of 12a (Fig. 2.19). The hydride ligand was arbitrarily positioned in
12a but was ultimately optimized as a Zr H Zr bridging hydride.
Figure 2.19. PW91PW91/LANL2DZ optimized structure of (C10H8)[CpZr]2(μ-H)(μ-Cl)(μ-GaR) (R = 2,6-Me2C6H3-) (12a)
In accordance with the molecular structure and computations, the structure of 12 can be
described as a trimetallic fulvalene-bridged dizirconocene-gallium complex with bridging
hydride and chloride ligands with a formula of (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR). The two
79
zirconium atoms have formal oxidation +4 states. This can be easily discerned by localizing the
hydride and chloride ligand on separate zirconium atoms (Fig. 2.21). The possibility of the
hydride atom residing on the Ga in 12 is highly unlikely due to two factors: 1) the trigonal planar
environment about the gallium atom; 2) the absence of a Ga H bond IR stretch (1800-200 cm-1).
Zr Zr
Ga
R
Cl
H
Zr Zr
Ga
R
Cl
H
12
Figure 2.20. ChemDraw representation of 12 depicting with bridging and localized chloride and hydride ligands
A closer inspection of the structure 12 shows that the Zr atoms are coordinated to Cp
ligands, as well as bridging RGa and Cl ligands, which affords a (μ-Ga)Zr2(μ-Cl) four-
membered butterfly (bent) core. The two zirconium atoms are also coordinated in a 5-fashion to
the fulvalene ligand and are held in close proximity (Zr Zr separation of 3.516 Å). This distance
is only slightly longer than the sum of zirconium covalent radii, 3.4 Å, suggesting minimal Zr Zr
contact. Computational studies, however, have suggested that through-space Zr···Zr interactions
may occur up to 4.25 Å.173
The structure of 12 also has several additional interesting features of note. Perhaps most
significant are the varying Ga Zr bond distances (Ga(1) Zr(1) 2.7457(9) Å and Ga(1) Zr(2)
2.8796(10) Å), which may be in large part due to steric crowding about the trimetallic centers.
As demonstrated in the space filling view of 12 (Figure 2.19), the m-terphenyl ligand extends
80
beyond the fulvalene ligand, causing considerable steric interactions. As a consequence, there are
close intramolecular C H···H C interactions between the fulvalene ligand and the flanking
phenyl rings (H(33A)···H(12A), 2.583 Å; H(33A)···H(11A), 2.785 Å). To lessen steric
congestion, it appears that the central phenyl ring of the m-terphenyl ligand assumes a skewed
conformation (63.41°) relative to the GaZr2 plane, instead of an orthogonal orientation. This
structural manifestation is not only apparent in the solid state but also in solution, as the low-
symmetry disposition of 12 is evident in its 1H NMR spectrum which displays two singlet signals
for the Cp ligands and eight well-resolved multiplets corresponding to the fulvalene ligand (two
ABCD spin systems).
Figure 2.21. Space filling model of (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12)
The Ga Zr bond distances in 12 are comparable to those bonds found in
[Li(THF)4][Cp2Zr{Ga[N(Aryl)C(H)]2}2] (Aryl = 2,6-i-Pr2C6H3-) (2.7417(7) and 2.7349(8) Å),149
however they are significantly longer than those in Cp2Zr(GaR)2 (R = 2,6-(2,4,6-i-
Pr3C6H2)2C6H3-) (2.6350(8) Å),146 which possesses Zr Ga -back-bonding. The Zr(1) Cl(1)
and Zr(2) Cl(1) bond distances in 12, 2.6033(13) and 2.6141(13) Å, respectively, are
81
unremarkable and compare with those in (C10H8)[(Cp)Zr(μ-Cl)]2 (2.568(2) and 2.591(2) Å).174
Perhaps expected, these bonds in 12 are longer than the terminal Zr Cl bonds in
(C10H8)[CpZrCl]2(μ-O) (2.471(1) Å).172 The Zr(1) Cl(1) Zr(2) bond angle (84.73(4)°) in 12 is
smaller than either of the Ga Zr Cl bond angles (92.76(4)° and 96.17(4)°) but slightly larger
than the analogous angles in (C10H8)[CpZr(μ-Cl)]2 (77.35° mean avg.)°. The Zr(1) Ga(1) Zr(2)
bond angle in 12 is 77.33(2)° and has no example to compare.
Returning to the DFT optimized structure of 12a reveals that it agrees well with the
experimental structure of the 12. There are some discrepancies, however, which is observed
when comparing the overall geometry. As previously suggested, the m-terphenyl ligand in 12 is
skewed with respect to the GaZr2 plane due to steric interaction. The structure of the 12a, which
contains a substantially less bulky 2,6-Me2Ph ligand, supports this proposal as the mesityl plane
is nearly perfectly orthogonal to the GaZr2 plane. Additionally, the Ga Zr bond distances
(2.7457(9) and 2.8796(10) Å) in 12 spans a greater range than those computed for the more
symmetrical and idealized 12a (2.842 and 2.839 Å). Certainly, the steric bulk of the m-terphenyl
ligand in 12 contributes to this manifestation.
2.3 m-Terphenyl Group 4 Metallocenes
2.3.1 Synthesis and Structure of Cp2TiR (R = 2,6-(4-Me-C6H4)2C6H3-) (13)
Sodium metal reduction of R 3In (R = 2,6-(4-Me-C6H4)2C6H3-)(7) in the presence of
Cp2TiCl2 gave the unexpected formation of a trivalent m-terphenyl stabilized titanocene
complex, Cp2TiR (13) (Eq. 2.7). Though the formation of 13 is not well understood, it is known
that triorganoindium, R3In,174 and indates, R4In-,175,176 are commonly utilized as nucleophilic
organometallic substrates in catalyzed and non-catalyzed cross coupling reactions of aryl halides.
82
The formation of 13 may follow a similar pathway, wherein ligand-halide exchange occurs
between R 3In and a Cp2TiCl intermediate. Unfortunately, the results of this experiment could
not be reproduced, usually giving only the titanocene monochloride dimer [Cp2TiCl]2.177
Ti
13
R 3In
(7)
Cp2TiCl2Na+
Monomeric trivalent cyclopentadienyl titanium(III) derivatives are very rare and only a
few unambiguously structurally characterized species have been reported.178-181 Furthermore,
only one of these structurally characterized compounds incorporates unsubstituted Cp ligands,
Cp2TiR (Cp = C5H5, R = Mes).178 Pursuing this compound was of interest due its novelty,
however a different synthetic approach would be required. We proposed that 13 could be
synthesized by direct reaction of R Li with [Cp2TiCl]2. Acquiring [Cp2TiCl]2 in adequate
quantities was approached by several literature techniques including aluminum182 and zinc177
metal reduction of Cp2TiCl2, however yields were low and purification/isolation protocols were
laborious. Lithium nitride (NLi3) reduction of Cp2TiCl2 with in THF was the most practical
means to synthesize [Cp2TiCl]2 in acceptable yields (50%) (Eq. 2.8).183 As predicted, R Li reacts
smoothly with [Cp2TiCl]2 to give green-brown crystals of 13 in good yield (50%) (Eq. 2.9).
(2.7)
83
1/3 Li3N, THFTi
Cl
ClTi
-1/6 N2, -3 LiCl
[Cp2TiCl]2
TiCl
Cl
Li Ti2 2-2 LiCl
+THF, -78°C
13
Ti
Cl
ClTi
The single X-ray crystal structure of 13 (Fig. 2.22) displays a trivalent titanocene in a
distorted trigonal planar titanium atom with respect to the Cp centroids, which is demonstrated
by summation of the exceptionally large Cp(centroid) Ti(1) Cp(centroid) bond angle (134.93°) and
the two equivalent C(1) Ti(1) Cp(centroid) bond angles (112.54°) to account for 360° around the
Ti atom. The sterically imposing m-terphenyl ligand adequately protects the labile metal center
and dwarfs the Cp ligands. The central phenyl ring of the ligand is aligned nearly orthogonal to
the Cp(centroid) Ti Cp(centroid) plane in an orientation that imposes a two-fold axis that passes
through the central phenyl ring and the titanium atom. The outer phenyl rings of the m-terphenyl
ligands are C2 symmetry related and have several close C H H C interactions with the CP
ligands (2.274 Å).
(2.8)
(2.9)
84
The Ti(1)-C(1) bond length in 13 of 2.242(2) Å is comparable to other trivalent
titanocenes such as Cp*2TiCH2CMe3 (Cp* = C5Me5) (2.231(5) Å)179 and Cp2TiR (R = 2,6-
Me2C6H3) (2.178(7) Å),178 and surprisingly similar to the tetravalent 17-electron complex,
Cp2Ti[2-((CH3)2NCH2)C6H4], (2.22(3) Å),180 but slightly shorter than those (2.332(2) Å) in 1-
C5H5)2(5-C5H5)2Ti.181
The trivalent nature of 13 and the of lack an observable counter ion are characteristic
features of 15-electron trivalent titanium species, Cp2*TiR (Cp* = Me5C5, R = aryl, alkyl,
halide). Hence, it is compelling to assign a d1 electron configuration to the titanium atom. The 1H
NMR spectrum of 13 shows a series of broad and ill-defined signals that were insufficient for
integration and characterization. The presence of a radical would undeniably cause such a
distortion. An ESR spectrum was recorded to rule out the possibility of an undetected hydride
and also to confirm the paramagnetic properties of 13. Two signals were observed in the ESR
spectrum of 13. The characteristic high-field singlet signal at g = 1.959 (line width 12 G) is
similar to those for other 15-electron titanium(III) species and confirms the paramagnetic nature
of 13, while the smaller low-field signal at g = 1.979 (line width of 6 G) is evidence of THF
coordination to the titanium center. The two signals may represent an equilibrium process
between the two species. A similar occurrence was observed for (C5HPh4)2TiCl.184 Though
sterically encumbered electron-deficient, 15-electron, monomeric Cp2*TiR compounds are
reluctant to dimerization or form adducts with solvents or salts, the titanium atom in 13, seems to
be accessible to donor solvents. This is a promising phenomenon for the possible utility of 13 to
serve as a one-electron reducing reagent or as a substitute for Cp2TiCl in pinacol185 and
McMurray186 coupling reaction protocols.
85
Figure 2.22. Molecular structure of Cp2TiR (13)
Table 2.13 Selected bond distances [Å] and angles [°] for Cp2TiR (13)
Ti(1) C(1) 2.242(2) Cp(centroid) Ti(1) Cp(centroid) 134.93
Ti(1) Cp(centroid) 2.059 C(1) Ti(1) Cp(centroid) 112.54
86
2.3.2 Synthesis and Structure of Cp2Zr(R)(Cl) (R = 2,6-(4-t-BuC6H4)2C6H3-) (14)
As demonstrated with 13, adequate steric protection about titanium may afford stable
monomeric trivalent Ti(III) radicals; however, this characteristic has thus far eluded zirconium.
Typically, trivalent zirconocene compounds are cationic complexes, [Cp2ZrR]+, which
commonly accept donor molecules,187,188 while zirconocene(III) halides tend to dimerize as
demonstrated in the dizirconocene complex [(C10H8)(ZrCp)2(μ-Cl)2].174 We hypothesized that a
Zr(III) radical could be synthesized by alkali metal reduction of a sterically crowded
Cp2Zr(R)(Cl) precursor. Our initial attempts to synthesize Cp2Zr(R)(Cl) (R = 2,6-(2,4,6-i-
Pr3C6H2)2C6H3-) were unsuccessful, perhaps due to excessive steric interactions between the Cp
rings and m-terphenyl ligand. Specifically, we postulated that substitution at the ortho-positions
of flanking phenyl rings did not allow the ligand to approach the Zr center, thus we selected a
ligand without such substitution. Indeed, reaction of RLi (R = 2,6-(4-t-BuC6H4)2C6H3-) with
Cp2ZrCl2 affords Cp2Zr(R)(Cl) (14) as colorless crystals (Eq. 2.10). We also proposed that the
corresponding titanium precursor, Cp2Ti(R )(Cl), was an interesting undertaking, as it would
provide an alternative route to 13 through alkali metal reduction. However reaction of R Li with
Cp2TiCl2 only gives the green [Cp2TiCl]2 species (Eq. 2.11). A similar occurrence was observed
when Cp2TiCl2 is allowed to react with i-PrMgBr.189 Thus, it appears that the nucleophilic
properties of R Li is dominated by its basicity.
Cp2ZrCl2 + RLi Cp2Zr(R)(Cl)
14
NaRH
(2.10)
Cp2TiCl2 + R Li [Cp2TiCl]2 (2.11)
87
To complete the final step to synthesize the elusive Zr(III) radical species, 14 was
reduced with sodium metal in toluene over three days to give a green solution (Eq. 2.10).
Unfortunately, only ligand hydrocarbon (R-H) could be isolated and no further attempts were
pursued. although the target molecule, Cp2ZrR , was not successfully synthesized, the single
crystal X-ray structure of its precursor 14 (Fig. 2.23) is interesting in its own right, as it is the
first m-terphenyl zirconium complex.
The structure of 14 provides a glimpse into the steric effects of the bulky m-terphenyl
ligand on zirconocene. As evidence of the wide C(1) Zr(1) Cl(1) and
Cp(centroid) Zr(1) Cp(centroid) bond angles, 118.79 and 130.73°, respectively, the four coordinate
zirconium atom adopts a trigonal pyramidal environment (Cp(centroid) Zr(1) Cl(1), 101.54 and
101.90°; Cp(centroid) Zr(1) C(1) 100.54 and 105.00°). The structure shows that the outer phenyl
rings on the m-terphenyl ligands are twisted (torsion angle = 80° av) from the central phenyl
rings, and the plane of central phenyl ring is slightly tilted (14°) out of co-planarity with
C(1) Zr(1) to lessen steric interactions with Cp ligands. Nevertheless, the ligands are separated
by less than 2.4 Å. This may also have an affect on the Zr(1) C(1) bond distance (2.380(4) Å),
which is significantly longer than the analogous bond distances in Cp2Zr(Cl)(CH2PMe2) and
Cp2Zr(Cl)(CH2PPh2), 2.272(6) and 2.317(5) Å, respectively.190 The Zr Cp(centroid) and
Zr(1) Cl(1) bond distances in 14 are 2.200 and 2.461(12) Å, respectively, and are generally
unremarkable.
In conclusion, although we could not successfully synthesize a stable monomeric
Zr(III)species, its precursor 14 joins a exceedingly small collection of zirconocene complexes
with a both halide and aryl substitution191 and the only m-terphenyl zirconocene.
88
Figure 2.23. Molecular structure of Cp2Zr(R)(Cl) (14)
Table 2.14 Selected bond distances [Å] and angles [°] for Cp2Zr(R)(Cl) (14)
Atoms Distance Atoms Angle Zr(1) C(1) 2.380(4) Cp(centroid) Zr(1) Cp(centroid) 130.73 Zr(1) Cl(1) 2.4612(12) C(1) Zr(1) Cl(1) 118.79(9)
89
2.4 Gallepins
Our research group has long had a fascination with the concept of aromaticity. Indeed,
our pioneering discoveries of the cyclotrigallenes, M2[Mes2C6H3Ga]3 (M = Na24 or K25; Mes =
2,4,6-Me3C6H2), were the first experimentally realized compounds to possess all metallic rings
that display traditional aromatic properties and transformed the initial concept of
metalloaromaticity. Aromatic species, wherein a metal moiety, MR, replaces a C H fragment of
an arene, have also been the subject of a number of studies.192-199 The exceptional work
conducted by Ashe demonstrated that a B R moiety can readily replace a C H fragment of an
aryl six-membered ring to give anionic six-membered aromatic BC5-boron-carbocycles known as
boratabenzenes.172,200-204 This strategy can also be extended to give borepins neutral seven-
membered BC6-boron-carbocycles that are isoelectronic with the tropylium ion.205-209 Besides
being structurally interesting, the boratabenzenes can serve as alternatives to cyclopentadienyl
substitutes for preparing novel transition metal “sandwich” complexes, which have been shown
to have surprising catalytic function in olefin polymerization reactions.210,211 On the other hand,
borepins may serve as 7-coordinating ligands for constructing interesting half-sandwiched
Cr209,212 and Mo207,208,213 complexes, however no catalytic activity has been documented utilizing
these complexes.
While the chemistry of aromatic borocarbocycles is quite developed, the analogous
chemistry of gallium is not. Perhaps the distinct electronegativity differences between gallium
and boron constitute this disparity. Though five-membered GaC4-heterocycles are fairly well
known,132,134-137,214 the gallatabenzene, RGaC5H5 (R = Mes), and its precursor, RGaC5H6, are the
only examples of six-membered gallium-carbocycles.215 A seven-membered gallium-carbocycle
remained unknown, hence synthesizing this elusive species seemed liked a worthy endeavor, as a
90
wealth of experimental, spectroscopic, computational, and chemical knowledge would be
obtained and would also provide an opportunity to evaluate the aromatic properties of the
tropylium ion when a C H fragment is replaced with a gallium moiety, Ga R. The borepins
have already proven to be aromatic, but how does gallium affect -electron delocalization? Its
larger atomic radius (1.30 Å) and metallic properties are central to this question. These seven-
membered gallium carbocycles would be isoelectronic with borepins and the tropylium ion
(cycloheptatrienyl cation, C7H7+),216,217 thus following established nomenclature, they will be
referred to as gallepins. The corresponding structures for the tropylium ion, borepin and gallepin
are shown in Figure 2.24.
Ga
X
Tropylium ion Gallepin
B
X
Borepin
Figure 2.24. Tropylium ion localized cation and delocalized cation, borepin, and gallepin
Though borepins are readily prepared by boron-tin exchange reactions of the respective
stannepin (R2SnC6R6) and organoboron dihalide derivative, RBX2 (Eq. 2.12), this has not been
effective strategy to synthesize gallepins; thus, a different approach would have to be embraced
to accomplish this undertaking.
Sn
RR
+ RBX2
- R2SnX2
B
R
(2.12)
91
This group’s previous syntheses of five-membered GaC4-heterometallacycles by
employing dilithium precursors in ring closure metathesis of gallium halides presented a
practical means to prepare gallepin derivatives.132,133Conceptually, ring closure of 1,6-dilithio-
hexa-Z,Z,Z-1,3,5-triene about GaCl3 should easily afford a gallepin (Eq. 2.13). Unfortunately,
there is no convenient synthetic report of the all Z-isomer. We speculated that a Z,Z,Z-trienyl
type system may be better stabilized by replacing the 1,2 and 5,6-olefin segments with phenyl
rings, providing in essence stilbene. Installing bromide atoms at the 2 and 2 positions of Z-
stilbene would allow for selective lithiation at these positions with n-BuLi to give access to the
dilithium derivative.
Li Li
GaCl3
Ga
Cl
X+
Auspiciously, Gilheany and coworkers have demonstrated that Z-stilbenes are the major
products of Wittig reactions when both the benzyltriphenylphosphonium salt, [PhCH2PR3]+, and
benzaldehyde, possess ortho-halogen groups.218 In accordance with Vedejs219-221 early
mechanism studies, they concluded that a phosphorous-bromide interaction occurs in the
transition state to create a “cooperative effect” that makes the Z-isomer preferential.
Indeed, 2,2 -dibromo-Z-stilbene (15) is conveniently prepared in good yield as large
colorless crystals by a two-step process (Eq. 2.14). The first step is an Arbuzov reaction of
triphenylphosphine and 2-bromobenzylbromide in refluxing toluene to give 2-
(2.13)
92
bromobenzyltriphenylphosphomium bromide, which is followed by addition of 2-
bromobenzaldehyde and sodium hydroxide. Surprisingly, the single crystal X-ray structure of 15
has not been reported and is shown in Figure 2.25. The structure of 15 is fairly direct and the
bond distances are as expected. The most interesting feature may be that the molecule is C2
symmetric.
Br
Br
PPh3
Br
PPh3
Br
+- OPPh3
Br Br2-bromobenzaldehyde3M NaOH
15
Toluene,
reflux, 4h
Figure 2.25. Molecular structure of 2,2 -dibromo-Z-stilbene (15)
With significant quantities of 2,2 -dibromo-Z-stilbene (15) in hand, the task became one
of obtaining the dilithio precursor. Initially, this step seemed routine and was pursued by reaction
with two equivalence of n-BuLi with 15. When the reaction is conducted in diethyl ether the
initial colorless solution of 15 turns orange upon addition of n-BuLi. Removal of all solvent
provides orange oily residues consisting of a mixture of products (determined by 1H NMR
(2.14)
93
spectroscopy) (Eq. 2.15). Alternatively, when the reaction is performed in hexane an orange
precipitate forms, which removal of solvent gives a pyrophoric orange powder that
spontaneously ignites in air (Eq. 2.15). Given that several single X-ray structures of dilithio
organometallic compounds incorporate TMEDA,222,223 it was thought that TMEDA may also be
useful at stabilizing the dilithio precursor. It was found that addition of TMEDA to the
pyrophoric orange powders in hexane/diethyl ether (10:1) gives orange-red crystals of the
dilithio precursor, 2,2 -dilithio-Z-stilbene(TMEDA)2 (16) (Eq. 2.15). Alternatively, 16 may also
be isolated by extraction of the orange oily residue with hexanes, followed by addition of
TMEDA (Eq. 2.18). If TMEDA is added to the diethyl ether parent solution, copious amounts of
[(TMEDA)LiBr]2 are formed and only minute quantities of 16 are secured (Eq. 2.15).
2 n-BuLi
Orange OilEt2O
HexaneOrange Powder
1) Et2O, 2) TMEDA16 + [(TMEDA)LiBr]2
1) Et2O, 2) hexanes
3) TMEDA 16
-78°C
15
(major product)
Compound 16 (Fig. 2.26) was examined by single crystal X-ray crystallography to
evaluate its structure and bonding, which revealed a Z-stilbenyl moiety bridged by two lithium
atoms at the C(1) and C(1A) positions to form a four-membered Li2-μ-C2 butterfly ring. Indeed,
Li2-μ-C2 butterfly cores have been a common structural manifestation for an array of TMEDA
stabilized ortho-dilithium biphenyl compounds.224-226 Computations suggest that this bonding
model is energetically favored as a consequence of electrostatic interactions.222,223,227 For
(2.15)
94
comparison purposes, the bonding arrangement in E-stilbenyl bis(lithium TMEDA)228 is
distinctly different from that in 16, as to be expected, because the anionic sites are at completely
different locales. Whereas in 16 intramolecular dilithium dimerization is stabilized because the
ortho-positions are anionic, the lithium atoms in E-stilbenyl bis(lithium TMEDA) are -
coordinated above and below the central ethylene segment of the E-stilbene moiety because the
two hydrogens on the olefin segment have been deprotonated.
There are several interesting structural features of 16 that merit discussion. Particularly,
the central C6 fragment in is nearly planar. To accommodate this configuration the
C(6) C(7) C(7A) bond angles (139.70°) are bent well past ideal trigonal planar geometry
(120°) and the phenyl rings are slightly puckered. A mirror plane bisects through the C(7) and
C(7A) atoms of stilbenyl olefin segment and the lithium atoms, however there are no rotation
axes. The coordination spheres about the lithium atoms assume tetrahedral geometry, afforded
by bridging the C(1) and C(1A) atoms of the stilbene ligand and chelation of the TMEDA
molecules. The Li(2) C(1) and Li(2) C(2) bond lengths are essentially equivalent (2.157(8) and
2.158(4) Å, respectively) and compare well with those of other ortho-dilithium biphenyl
compounds (2.147-2.166 Å).224-226 The anionic carbons are in a seriously distorted tetrahedral
environment, and they are well separated at a distance of 3.326 Å.
95
Figure 2.26. Molecular structure of 2,2 -dilithio-Z-stilbene(TMEDA)2 (16)
Table 2.15 Selected bond distances [Å] and angles [°] for 2,2 -dilithio-Z-stilbene(TMEDA)2 (16)
Atoms Distance Atoms Angle Li(1) C(1)#1 2.158(4) C(1)#1 Li(1) C(1) 100.8(3) C(1) C(2) 1.405(3) C(1)#1 Li(2) C(1) 100.9(3) Li(1) N(2) 2.155(6) C(1) Li(1) Li(2) 54.13(14) Li(1) N(1) 2.194(7) N(2) Li(1) N(1) 84.0(2) Li(1) Li(2) 2.527(8) N(3) Li(2) N(4) 83.9(2) Li(2) N(3) 2.187(7) C(1) C(6) C(7) 124.9(2) Li(2) N(4) 2.247(6) C(7)#1 C(7) C(6) 139.70(12)
96
The isolation of 16 proved that 2,2 -dibromo-Z-stilbene could be selectively lithiated by
salt metathesis reactions, and that although a mixture of products, the orange oils and pyrophoric
powder contained the “TMEDA-free” dilithium species. The reactivity of the “TMEDA-free”
orange oil and pyrophoric powder with GaCl3 was evaluated to determine if TMEDA
stabilization was necessary to isolate the gallepin. Perhaps as expected, these reactions generally
gave viscous impure yellow oils. The 1H NMR spectra of these oils were too complex to be
adequately useful for characterization, as a multitude of peaks were observed in the aromatic
region (6.5-8.0 ppm). Purification by distillation was not attempted due to concerns of destroying
the thermolabile Ga C bonds. After considerable synthetic effort, however, poor quality
colorless crystals covered with yellow oil were isolated from reaction of the orange oil with
GaCl3 (Eq. 2.16). The crystals were suitable for single crystal X-ray analysis and were ultimately
determined to be a spirogallate, (spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)] (17). The single
crystal X-ray structure of 17 (Fig. 2.27) has two very similar molecules in one asymmetric unit
thus only one will be discussed.
Br Br
2 n-BuLiOrange Oil
-78°C
GaCl3Hexane,-78C°
Ga
Li
Et2O
17
15
(2.16)
97
Figure 2.27. Molecular structure of [spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)] (17)
Table 2.16 Selected bond distances [Å] and angles [°]
for [spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)] (17)
Atoms Distance Atoms Angle
Ga(1) C(1) 1.972(4) C(33) Ga(2) C(42) 108.64(19)
Ga(1) C(15) 1.987(4) C(47) Ga(2) C(56) 106.96(16)
Ga(1) C(10) 2.022(4) C(56) Ga(2) C(42) 109.33(15)
Ga(1) C(24) 2.030(4) C(47) Ga(2) C(33) 117.54(19) Ga(1) Li(1) 2.722(9) C(56) Li(2) C(42) 91.1(3)
98
The structure of 17 reveals a spirogallate anion with a central four-coordinate gallium
atom engaged in bonding with two puckered Z-stilbenyl moieties. Compound 17 is notable as
only the second spirogallate and the only report of a “spirogallepin”. A distortion to ideal
tetrahedral geometry about the gallium is apparent by the C(47)-Ga(2)-C(33) (117.54(19)°) bond
angle. The remaining bond angles about gallium are close to expected. The anionic nature of the
gallate ion is countered by a lithium cation that is coordinated to the C(42) and C(56) atoms of
opposing stilbenyl fragments (C Li bonds distances, 2.305(9) Å) to form a “diamond like” four-
membered GaC2Li ring. Indeed, the heteroatomic ring is quite distorted due to variance in bond
angles. While both of the Ga C Li bond angles are close to 80°, the C(42) Ga(2) C(56) and
C(42) Li(2) C(56) (109.33(15)° and 91.1(3), respectively), vary significantly, by more than 20°.
The Li atom assumes trigonal planar geometry by coordinating to the opposing stilbenyl ligands
and a molecule of diethyl ether. The Ga C bond distances in 17 range from 1.972(4) to 2.030(4)
Å and compares well with those in the first spirogallate, [{(PhC=CPh)2}2Ga][Li(THF) 12-
crown-4] (2.001(5)-2.023(5) Å)133 and the five-membered gallate heterocycle
[{(PhC=CPh)2}GaCl2][Li2(OEt2)4] (1.966(4) Å).132 Due to the flexibility of the Z-stilbenyl
ligands in 17 the interannular C Ga C bond angle (C(47) Ga(2) C(56) and
C(33) Ga(2) C(42), 108.64(19)° and 106.96(16)°, respectively) of the GaC6-seven-membered
rings are considerably larger than the corresponding C Ga C bond angles reported for five-
membered GaC4 heterocycles (87.4 - 91.4°). Interestingly, when 17 is recrystallized in diethyl
ether the Li coordination to the stilbenyl ligands is disrupted to give a slightly different species,
[spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)3], (17a). (Eq. 2.17). The molecule maintains the
essential elements of 17, but the lithium cation is far removed and surrounded by three diethyl
ether molecules.
99
Ga
Li
Et2O
17
Recrystallize, Et2OGa
17a
Li(OEt2)3
Though the isolation of 17 is a significant result, its formation denotes the importance of
correct stoichiometric ratios of the dilithio precursor and GaCl3. Not only is it integral to ensure a
single ring closure about the gallium atom, but also it would also likely reduce the probability of
side products formed in the reaction. Thus, obtaining a pure sample of the dilithium reagent is of
utmost importance. Utilizing 2,2’-dilithio-Z-stilbene(TMEDA)2, 16, for the ring closure about
GaCl3 seemed promising because it is a pure, solid, crystalline material, and easily handled (not
pyrophoric). Indeed, allowing 16 to react with GaCl3 in diethyl ether gave large colorless crystals
of bis(gallepin)2·TMEDA (18) (Eq. 2.18) in good yield (60%).
1) 2 n-BuLi
2) TMEDA16
GaCl3, Et2O
-78°C 18
Br Br
(2.18)
15
The crystal structure of 18 (Fig. 2.28) provides a compelling view of the first gallepin.
The structure shows two gallepins bridged on opposite ends of a “stretched-out” TMEDA
molecule. Although not easily discerned, 18 is C2 symmetric about the center of the TMEDA
(2.17)
100
molecule. The gallepin moieties adopt a “boat-like” conformation instead of planar, with the
phenyl rings pointed in one direction, while the gallium atom and olefin segment in the other. A
detailed evaluation of the pseudo-tetrahedral four coordinate gallium atoms show that they reside
0.58 Å above the central C(1) C(6) C(9) C(10) plane at an angle of 35°. Similar to that in 17,
the GaC6-seven-memebered rings show significant signs of angle strain, as the C(6) C(7) C(8)
and the C(7) C(8) C(9) bond angles (137.45(17)° and 137.93(18)°, respectively) of the olefin
segment are substantially larger than expected for sp2-hybridized carbons. The Ga(1) C(1) and
Ga(1) C(10) bond distances, 1.9476(17) Å and 1.9477(18) Å, respectively, are as expected and
comparable to those bond distances for other gallium heterocycles (1.934-2.164 Å).
Figure 2.28. Molecular structure of bis(gallepin)2·TMEDA (18)
101
Table 2.17 Selected bond distances [Å] and angles [°] for bis(gallepin)2·TMEDA (18)
Atoms Distance Atoms Angle
Ga(1) C(1) 1.9476(17) C(1) Ga(1) C(10) 117.94(7) Ga(1) C(10) 1.9477(18) C(1) Ga(1) N(1) 104.64(6)
Ga(1) N(1) 2.1158(15) C(10) Ga(1) N(1) 108.99(7)
Ga(1) Cl(1) 2.2258(5) C(10) Ga(1) Cl(1) 112.29(5)
Several structural features of the gallepin moieties in 18 are counterintuitive to elicit
aromatic properties, i.e., 1) the puckered boat-like conformation of the gallepin moieties, 2) the
alternating C C bond distances (1.41, 1.46, 1.35 Å av.), and 3) the coordinating amine. In an
effort to better assess aromaticity and compare structures, computations were performed on two
simpler models: 18Cl(NMe3) and 18Cl (Fig. 2.29). In the 18Cl(NMe3) model compound the
TMEDA molecule in 18 is replaced with trimethylamine (NMe3), whereas 18Cl is free of amine
coordination. The B3LYP/LANL2DZ optimized bond lengths and angles of the models are in
reasonable agreement with 18. There are, however, a few discrepancies worthy of discussion.
Most significant is that the conformations of the two structures differ dramatically. While
18Cl(NMe3) adopts a boat-like conformation, 18Cl is essentially planar, which suggest the
puckered conformation found in 18 is a result of the N Ga interaction. Furthermore, the
computed Ga C bonds lengths (1.920 Å) in 18Cl are slightly shorter than those in 18
(1.9476(17) Å), while those in 18Cl(NMe3) are comparably longer (1.958 Å). Though the
shorter Ga C bond lengths in 18Cl may be expected due to lack of amine coordination, the
variance of these bond distances between 18 and 18Cl(NMe3) was unexpected because they are
essentially identical. Perhaps, the greater Lewis basic properties of NMe3 attributes to this
structural feature. More surprising, the computed Ga Cl bond distance (2.230 Å) for 18Cl is
essentially identical to that in 18 (2.2258(5) Å), whereas that computed for 18Cl(NMe3) (2.121
Å) is significantly shorter by 0.1 Å.
102
Figure 2.29. B3LYP/LANL2DZ optimized geometries of 18Cl(NMe3) and 18Cl.
Nucleus-independent chemical shifts (NICS)106 were computed at the IGLO-
PW91/IGLOIII level to assess aromatic character in 18Cl(NMe3) and 18Cl. In addition, as only
the perpendicular (zz) tensor -MO contributions are utilized, the NICS zz index was employed
to better assess ring current. Full details of these NICS calculation are shown in Table 2. 18. The
positive NICS values for the GaC6-seven-membered rings in 18, 18Cl(NMe3), and 18Cl (2.6,
1.9, and 1, respectively) are indicative of non-aromatic character, however, the NICS zz values
substantiate the presence of ring current (18Cl(NMe3) = -9.9, 18Cl = -9). The minute difference
in NICS zz values between 18Cl(NMe3) and 18Cl suggest that amine coordination has minimal
effect on the degree of -electron delocalization.
For purposes of comparison, NICS calculations on an unsubstituted base-gallepin without
phenyl rings, HGaC6H6, (NICS(0) = -2.3, NICSpzz = -15.3) shows that its values are much more
negative than those in 18Cl(NMe3) and 18Cl and suggest substitution significantly lowers the
aromatic properties. As illustrated in Table 2.19, the NICS values for the phenyl rings in these
species (-5.5, -7.2, and -8, respectively) are considerably more negative than the central GaC6-
18Cl(NMe3) 18Cl
103
seven-membered rings and thus more aromatic. This is a well-known effect of benzannulation,
wherein the more aromatic phenyl rings siphons more -electrons from the lesser aromatic
fragment. Moreover, comparison of the NICSpzz values for the base gallepin (HGaC6H6) and
borepin (HBC6H6), -15.3 and –27.7, respectively, imply that gallepins are innately less aromatic
than borepins.
To conclude, the first spirogallepin (17) and gallepin (18) were synthesized via a
benzannulation approach. NICS(0) and NICS zz calculations on models of 18, 18Cl and
18Cl(NMe3), suggest that these compounds are somewhat aromatic and that amine coordination
has minimal effect on ring current. Moreover, the more negative NICS values calculated for
HGaC6H6 implies that the phenyl rings attached the GaC6 ring in 18Cl and 18Cl(NMe3) greatly
diminishes their aromatic properties. It was also concluded by NICS calculations that gallepins
as a whole are substantially less aromatic than either the borepin or tropylium ion. This is most
likely due to the due to large atomic radius of gallium and thus poor orbital overlap of the Ga C
bond, which impedes electron delocalization.
Table 2.18. NICS, NICS , and NICS zz for seven-membered rings
of 18, 18Cl(NMe3), 18Cl, Gallepin, and Borepin Compound NICS NICS NICS zz
18 2.6 N/A N/A 18Cl(NMe3) 1.9 -5.3 -9
18Cl 1 -6.6 -9.9
Gallepin -2.3 -10.5 -15.3 Borepin -4.4 -15.1 -27.7
104
Table 2.19. NICS, NICS , and NICS zz for phenyl rings in 18, 18Cl(NMe3), and 18Cl Compound NICS NICS NICS zz
18 -5.5 N/A N/A 18Cl -7.2 -19 -32.7 18Cl(NMe3) -8 -19.5 -34.1
2.5 Examinations of Carbenes in Group 13 Chemistry
2.5.1 Introduction
Carbenes, R2C:, are neutral compounds containing a sp2-hybridized divalent carbon with
a sextet of electrons (Fig 2. 30). Fischer229,230 and Schrock230,231 type carbenes have been
thoroughly studied and are usually encountered in transition metal complexes, while in organic
chemistry carbenes can be traced back as far as the 1950’s, where they were hypothesized as
intermediates in certain mechanisms for reactions such as Simmons-Smith reactions.232 It was
not until Arduengo’s pioneering synthesis and molecular structure determination of 1-3-di-1-
adamantylimidazol-2-ylidene (Arduengo’s carbene) (Fig 2.30) in 1991, that a stable,
independent, and “bottle-able” carbene was experimentally realized.233
C
general carbenesinglet state
N NAd Ad
Ad =
Arduengo’s carbene
Figure 2.30. General carbene shown as singlet state and Arduengo’s carbene the first structurally characterized carbene.
The key to Arduengo’s carbenes stability lies in attractive steric effects of the adamantyl
ligands and the beneficial electronic effects the two -nitrogen atoms. Specifically, the authors
noted that the bulky adamantyl ligand provides adequate steric protection for the nucleophilic
105
center to deter dimerization, while from an electronic perspective, a “push-pull” mechanism
balances the dual disposition of the carbene center. To elaborate, a stabilizing effect occurs
wherein the -donor substituents (nitrogen) donate electrons into the “out-of-plane” empty p-
orbital, while simultaneously withdrawing electron density from the singlet pair of “in-plane”
electrons through -electronegativity effects (Fig. 2.31). Though these carbenes contain an
empty p-orbital, computational studies have shown that they are poor -back bonding acceptors
and the -donor properties dominates.234
N
-donation
N
N
electronegativity -effect
R
R
Figure 2.31. General N-heterocyclic carbene depicting electron withdrawing effects of the -nitrogen and -donation into the empty p-orbital of carbenic carbon
Arduengo-type carbenes are formally known as imidazol-2-ylidenes, but they have taken
on the common name of N-heterocyclic carbenes (NHCs). They have been thoroughly studied
and a wide variety of substituents may be placed at the nitrogen atoms and on the imidazole
backbone.235-237 The primary use of these carbenes has been to stabilize low-valent transition
metal complexes in place of phosphine ligands, which has proven to enhance catalytic activity in
olefin polymerizations and ring opening and closing metathesis reactions.234 More recently they
have also been employed as potent organocatalysts for a number of transformations.238 Although
carbenes are important components in catalytic systems, in regards to group 13 chemistry, they
106
present a convenient means to stabilize highly reactive trivalent compounds, and several
carbene group 13 complexes have been prepared.239-244 We wished to further explore carbenes
on group 13 elements to understand its effect on structure and bonding, and also its viability to
stabilize group 13 metal metal bonds.
It was predicted that by employing carbenes with substantial steric bulk on group 13
elements, neutral group 13 triple bonds could be synthesized. Since all three valence electrons of
the metal would be available for bonding, upon alkali metal reductions of organometallic group
13 trihalide adducts, (L:)EX3 (L: = carbene, E = group 13 element, E = halide), there would be no
need for electron donation from alkali metals to stabilize group 13 E E triple bonds. This project
was motivated by the objections to the gallium gallium triple bond formulation for the digallyne,
Na2[RGa GaR] (R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-) (Fig. 1.13),21 and specifically, the role of the
sodium atoms.84-86 The opposing authors have suggested that sodium is critical to the stability of
the digallyne, as reduction of RGaCl2 with potassium provides a structurally different complex
containing a Ga4 ring, K2[Ga4R2] (R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3) (Fig. 1.18), as opposed to a
potassium stabilized digallyne “K2[RGa GaR]”.22 If a neutral gallium gallium triple bond
could be stabilized without alkali metal electron donation, it would provide an opportunity to
compare and contrast its structure with the digallyne, Na2[RGa GaR].
Our preliminary efforts in this regard were aimed at boron, however when (L:)BBr3 (L: =
:C{N(2,6-PriC6H3)CH}2) is reduced with potassium graphite in diethyl ether a boron boron
triple bond is not obtained, but instead the first neutral compound containing boron boron
double bond (diborene), R(H)B=B(H)R, is produced.245 This compound contained the shortest
B=B double bond (1.561(18) Å) on record with an essentially planar C B=B C core.245 The
107
unexpected formation of the diborene, as oppose to triple bond formation, was attributed to
hydrogen abstraction from the ethereal solvent. Similarly, potassium graphite reduction of
(L :)BBr3 (L : = :C{N(2,6-Mes)CH}2), utilizing a less bulky carbene, also gave a neutral
diborene, L :(H)B=B(H):L , however this compound showed exceptional conformational
flexibility, as three different polymorphic structures in the solid state were determined by single
crystal X-ray analysis with twisted, planar, and trans-bent geometries.246 Though the
boron boron triple bond was obtained from these reactions, it showed that the carbene
interaction with the boron atom is strong enough to persist through relative harsh reductive
conditions.
Extending this chemistry to the heavier group 13 elements, however, was met with
disappointing results, as alkali metal reductions of (L:)EX3 (E = Al, Ga, In) gave only free
carbene and group 13 metal. The carbene ligand appears to have less affinity for the metallic
heavier group 13 members, which may be attributed to the large atomic radius of these elements
that impedes good orbital overlap with the smaller carbenic carbon. We hypothesized that by
augmenting the carbene-group 13 complexes with a C E -bond, cleavage of the L: E bond
would be deterred during reductions, due to a higher oxidation state and enhanced steric
protection. Mesityl was selected as a viable candidate to utilize in these studies due its attractive
steric qualities and the commercial availability of mesitylmagnesium bromide (MesMgBr). An
initial attempt to synthesize MesGaCl2(:L) (L: = :C{N(2,6-PriC6H3)CH}2) was performed by
reaction of the (L:)GaCl3 adduct with MesMgBr, however this method proved unsuccessful as
only starting material, (L:)GaCl3, was isolated (Eq. 2.19). Alternatively, we attempted to prepare
MesGaCl2(:L) by reaction of the carbene (L:) (L: = :C{N(2,6-PriC6H3)CH}2) with MesGaCl2,
however this reaction also lead to the formation of (L:)GaCl3 (Eq. 2.19). Evidently the steric
108
pressure around the gallium atom is too severe to accommodate both the mesityl ligand and the
large carbene ligand. Moreover, it appears that carbene gallium trichloride adduct formation is
preferred over maintaining or forming new Ga C -bonds, as (L:)GaCl3 is the lone product
isolated from either of the described reactions. This is probably not surprising since the dative
nature of the carbene ligand is a favorable interaction for GaCl3 as it provides a full octet of
electrons about the gallium atom, whereas it is well known that Ga C -bonds are highly labile
and sensitive to protolysis. This was also demonstrated by Nolan and coworkers, who have
shown that several carbene gallium trichloride complexes (L:)GaCl3 (L: = :C{N(2,6-
Pri2C6H3)CH}2, :C{N(2,4,6-Me3C6H3)CH}2, :C{N(i-Pr)C(Me)}2) can be store in air without
decomposition over a period of months in high humidity.244
GaCl3 MgBr+
GaCl3
N
N
Ga
X
GaCl2
X
X
X
N
N N
N
+
N
N
We then considered utilizing smaller carbenes for this study. Specifically, using a carbene
with only isopropyl functionality (L: = :C{(i-Pr)NC(Me)}2), in place of the 2,6-(di-i-
propyl)phenyl ligands,237 would lessen steric hindrance between the carbene and mesityl ligands
in the MesGaCl2(:L) complex. The condensation of 1,3-diisopropyl-2-thiourea with 3-hydroxy-
(2.19)
109
2-butanone to give the 1,3-diisopropyl-4,5-dimethylthioimidazole, followed by reduction with
potassium metal provides this ligand in good yield (Eq. 2.20). Indeed, reaction of this smaller
carbene (:L) with MesEX2125,247 (Eq. 2.21) gives Lewis base adducts of the general formula
MesEX2(:L), 19-21 (19, E = Ga, X = Cl; 20, E = Al, X = Br; 21, E = In, X = Br).
S
NH
NH
+
O
OH
hexanol, N N
S
K, THF N N
EX2 +N N
E
N
N
XX
19; E = Ga, X =Cl
20; E = Al, X = Br
21; E = In, X = Br
Although we synthesized the first organo-group 13 metal carbene complexes,(L:)ER3,
(M=Al, Ga, R = Me) more than a decade ago,239 compounds 19-21 are notable as the first
carbene stabilized organo-group 13 dihalides. In all cases complexes 19-21 are remarkably more
stable than the ‘free” mesitylgroup 13 dihalides, MesEX2, or carbene and can be exposed to air
without apparent signs of decomposition. Compounds 19 and 20 are insoluble in most organic
solvents, whereas 21 is highly soluble in toluene. However, all of these compounds are readily
dissolved in dichloromethane.
Colorless crystals of 19-21 are grown in a mixture of CH2Cl2 and THF. When neat
solvents are used for crystallization only amorphous materials are obtained. Although the crystal
structures of 19-21 are isostructural, they are not isomorphous. Both 19 and 20 are monomeric
(2.20)
(2.21)
110
carbene-organogroup 13 adducts, whereas compound 21 co-crystallizes with a molecule of
(L:)InBr3. There are two molecules of 19 in its asymmetric unit (triclinic P-1), whereas in 20
only one molecule is unique for the asymmetric unit (monoclinic C2/c).
The single crystal X-ray structures of 19-20 are depicted in Figures 2.32-2.34,
respectively, and they share several interesting features. All have four-coordinate group 13 metal
centers with distorted tetrahedral environments. The mesityl group 13 C E bond distances
(Ga(1) C(1) 1.978(2) Å, Al(1) C(1) 1.989(3) Å, In(1) C(12) 2.170(13) Å) are comparatively
shorter than the carbene group 13 E :L bond distances (Ga(1) C(10) 2.048(2) Å, Al(1) C(10)
2.050(3) Å, In(1) C(1) 2.224(10) Å). The average bond length difference between the two types
of E C bonds is 0.06 Å and denotes the weaker dative nature of the carbene group 13 metal
interactions.
Another notable feature of these compounds is the orientation of the two ligands, as the
carbene ligand is situated roughly orthogonal to the mesityl plane. This is obviously a preferable
arrangement to lessen steric interactions. Nevertheless, steric repulsion is still detected in the
C E C bond angles in 19 and 21 (19, C(1) Ga(1) C(10) = 119.14(9)°; 21, C(1) In(1) C(12) =
119.1(4)°), which is severely distorted from the expected value (109.5°) for tetrahedral
geometry. In contrast, the C(1) Al(1) C(10) bond angle (111.10(13)°) in 20 precludes this
structural feature, however the C(1) Al(1) Br(2) bond angle (119.11(13)°) is exceedingly large.
The X-ray structure (Fig. 2.32) of 19, MesGaCl2(:L), shows that the Ga C(carbene) bond
length (Ga(1) C(10), 2.048(2) Å) is much longer than those reported for other carbene-gallium
trichloride complexes, (L:)GaX3 (L = carbene, X = halide) (1.954-2.016 Å).244 This is most
likely due to the bulky mesityl ligand incorporated into 19, which impedes a closer interaction of
the carbene to the metal. This may also lend some validity to why the Ga(1) C(10) bond in 19 is
111
shorter to than (2.13 Å) that in (L:)GaMe3 (L: = :C{(i-Pr)NC(Me)}2239, which has three bulky
methyl groups surrounding the gallium.
The Ga(1) C(10) bond length in 19 is also slightly shorter than the Ga C bond length
(2.070(7 )Å) in the unsymmetrical carbene stabilized digallane, (L:)GaI2GaI2 (L: = :C{N(2,6-
PriC6H3)CH}2),248 which may be attributed to a number of reasons such as the lower oxidation
state of the gallium atom, and/or the large size and electronegativity of iodine in the latter.
Though the Ga Cl bond distances (2.246 Å av) of 19 are comparable to the associative bond
distances (2.19 Å av) in (L:)GaCl3 (L: = :C{(i-Pr)NC(Me)}2), which utilizes the identical
carbene, they are almost 0.5 Å longer that those of other reported carbene-gallium trichloride
complexes containing more bulky carbenes: ((L :)GaCl3, L : = :C{N(2,6-PriC6H3)CH}2, Ga Cl
2.173 Å); (L :)GaCl3, L : = :C{N(2,4,6-Me3C6H3)CH}2, Ga Cl 2.175 Å).244
Only a few carbene-stabilized aluminum compounds exist, thus it is prudent to discuss
similarities and differences between these complexes and 20, MesAlBr2(:L) (Fig. 2.33). All of
these complexes contain the expected tetrahedral four-coordinate aluminum atoms, however
there are slight differences in the Al C bond lengths. For example, the carbene-aluminum bond
length of (Al(1) C(10) = 2.050(3) Å) in 20 is substantially longer than that (2.0009(5) Å) in
(L*:)AlCl3 (L*: = :C{(Me)NC(Me)}2),243 perhaps due the smaller methyl groups at the nitrogen
sites on the carbene in (L*:)AlCl3, which allows a closer approach to aluminum. The Al C bond
distance (2.0034 Å) in carbene-stabilized alane, (L :)AlH3 (L : = :C{N(2,4,6-Me3C6H3)CH}2) is
also shorter than that in 19, however, in the more crowded (L:)AlMe3 (L: = :C{(i-Pr)NC(Me)}2),
the Al C bond distance (2.062(7) Å) is longer.239 A lengthening of the Ga C bond was also
observed when comparing 19 with the analogous carbene-stabilized trimethyl gallium complex,
(L:)GaMe3. There are no carbene aluminum tribromide adducts to compare with 20, however the
112
Al(1) Br(1) and Al(1) Br(2) bond distances, 2.3364(10) and 2.3373(10) Å, respectively, are
longer than those (2.297(3) and 2.302(3) Å) found in the m-terphenylaluminum dibromide
etherate 3, RAlBr2(OEt2) (R = 2,6-(4-t-BuC6H4)2C6H3-), but are more comparable to those in the
lithium bridged m-terphenylaluminum bromide dimer [RAlBr3Li]2, (R = 2,6-Mes2C6H3), (2.347
Å av).119
Figure 2.32. Molecular structure of MesGaCl2(:L) (19) Table 2.20 Selected bond distances [Å] and angles [°] for MesGaCl2(:L) (19)
Atoms Distance Atoms Angle
Ga(1) C(1) 1.978(2) C(1) Ga(1) C(10) 119.14(9) Ga(1) C(10) 2.048(2) C(1) Ga(1) Cl(2) 114.96(7)
Ga(1) Cl(2) 2.2444(6) C(10) Ga(1) Cl(2) 98.86(6)
Ga(1) Cl(1) 2.2468(6) C(1) Ga(1) Cl(1) 109.34(7)
Cl(2) Ga(1) Cl(1) 101.71(3)
113
Figure 2.33. Molecular structure of MesAlBr2(:L) (20) Table 2.21 Selected bond distances [Å] and angles [°] for MesAlBr2(:L) (20)
Atoms Distance Atoms Angle
Al(1) C(1) 1.989(3) C(1) Al(1) C(10) 111.10(13)
Al(1) C(10) 2.050(3) C(10) Al(1) Br(1) 114.61(9)
Al(1) Br(1) 2.3364(10) C(1) Al(1) Br(2) 119.11(10) Al(1) Br(2) 2.3373(10) C(10) Al(1) Br(2) 97.78(9)
Br(1) Al(1) Br(2) 104.53(4)
114
A closer inspection of the unit cell of 21, MesInBr2(:L), (Fig. 2.35) shows that there are
two Br3In(:L) molecules residing in between two MesInBr2(:L) complexes, and there are no
intermolecular contacts between the molecules. Only one of the sets represents the asymmetric
unit. An explanation for the formation of (L:)InBr3 is that unreacted InBr3, which is difficult to
remove from MesInBr2, reacts with the carbene. Nevertheless, it is still quite interesting that the
two molecules crystallized together. Since the crystal structure of Br3In(:L) has been previously
reported, it will not be discussed.249
An interesting feature can be observed along the In(1) C(12) bond in 21, wherein the
mesityl phenyl plane is slightly bent at an angle of 14°. The crystal structure of RAlBr2(OEt2) (3)
showed a similar distortion and was ascribed to packing forces; perhaps these forces are at play
in 21. The In(1) C(1) bond distance (2.224(10) Å) in 21 is somewhat longer than that (2.199(5)
Å) in the “mesityl-free” carbene indium tribromide adduct in (L:)InBr3,249 but compares well
with those of the dicarbene indium trihalide congeners, (L:)2InX3 (X = Cl, In C = 2.220(10) and
2.236(9) Å, X = Br, In C = 2.230(10) and 2.231(10) Å). Clearly the steric crowding about the In
atom in 21 causes the lengthening in the In C bond. The In Br bond distances (2.55 Å av) in 21
lie in between the range of those reported for (L:)InBr3 (2.50 Å av) and (L:)2InBr3 (2.69 Å av).
115
Figure 2.34. Molecular structure of MesInBr2(:L) (21) Table 2.22 Selected bond distances [Å] and angles [°] for MesInBr2(:L) (21)
Atoms Distance Atoms Angle
In(1) C(12) 2.170(13) C(1) In(1) C(12) 119.1(4)
In(1) C(1) 2.224(10) C(12) In(1) Br(2) 119.0(3)
In(1) Br(2) 2.5365(16) C(1) In(1) Br(2) 102.0(3)
In(1) Br(1) 2.5630(17) C(1) In(1) Br(1) 102.8(3)
Br(1) In(1) Br(2) 101.66(6)
116
Figure 2.35. A view of the unit cell of [MesInBr2(:L)][InBr3(:L)] (21) showing that there are no intramolecular contacts between the four molecules.
2.7.2 Alkali Metal Reductions of MesEX2(:L)
The isolations of neutral diborenes by alkali metal reduction of (L:)BBr3,
245,246 prompted
an examination of reductions of 19-21 with the intent to synthesize analogous neutral compounds
possessing double bonds of the heavier group 13 elements. Sodium metal reductions of 20 and
21 generally gave yellow viscous oils that could not be adequately characterized. In contrast,
potassium reductions of MesGaCl2(:L) (19) gave solutions that varied in color depending on
reducing agent and solvent. Specifically, potassium graphite (KC8) reduction of 19 in hexane
gave a pale yellow-orange solution (Eq. 2.22), which after work-up and removal of almost all
solvent, a yellow sticky oil was retained. Placing the oil at room temperature over several days
117
afforded pale yellow crystals of [MesGaCl(:L)]2 (22) in low yield. The low yield prevented
complete characterization (EA). Fortunately, the crystals of 22 were suitable for single crystal X-
ray crystallographic analysis.
2 KC8, hexane2 MesGaCl2(:L)
-2 KCl
2219
[MesGaCl(:L)]2
(2.22)
The crystal structure of 22 (Fig. 2.36) displays two four-coordinate gallium atoms, which
assume distorted tetrahedral geometry, held together by a Ga Ga bond. Several other structural
aspects of 22 merit comment. Perhaps most compelling is the Ga Ga bond distance (2.4474(11)
Å). For comparison purposes, this bond distance is similar to the corresponding Ga Ga distances
in the gallium(II)-amidinate complexes [GaI(MeC(NAr)]2 and {GaI(HC(NAr)]2 (Ar = 2,6-
Pri2C6H3-) (2.4304(10) and 2.4527(15) Å, respectively), which also contain four-coordinate
gallium atoms.250 Contrary, the Ga Ga bond distance (2.4739(12) Å) of the only other carbene
stabilized digallane, (L:)GaI2GaI2 (L: = :C{N(2,6-PriC6H3)CH}2) is significantly longer than that
in 22. Another notable feature of 22 is the C Ga C bond angles, (C(1) Ga(1) C(12), 106.7(3)°,
C(21) Ga(2) C(32), 103.0(3)°, which are substantially smaller than the corresponding bond
angle in MesGaCl2(:L) (19) (C(1) Ga(1) C(10), 119.14(9)°). One may consider that steric
repulsion between the ligands on the adjacent gallium atom in 22 causes contraction of geminal
ligands and limits conformational freedom. Evidence for this proposition may be supported by
the larger than expected C(12) Ga(1) Ga(2) and C(21) Ga(2) Ga(1) bond angles (132.2(2) and
122.57(19)°, respectively) and the Ga(1) C(1) and Ga(2) C(21) bonds distances, 2.101(7) and
2.084(7) Å, respectively, which are 0.045Å longer than that in 19 (2.045(2) Å)
118
A particularly intriguing aspect of 22 is the four different substituents about the gallium
atoms, which should allow for the possibility of diastereomers. However, a closer inspection of
22 shows that there is an center of inversion. Nevertheless, to our knowledge there are no
diastereomeric digallanes and 22 is the first meso-digallane.
Figure 2.36. Molecular structure of [MesGaCl(:L)]2 (22) Table 2.23 Selected bond distances [Å] and angles [°] for [MesGaCl(:L)]2 (22)
Atoms Angle Atoms Angle Ga(1) C(12) 2.028(7) C(12) Ga(1) Ga(2) 132.2(2) Ga(1) C(1) 2.101(7) C(1) Ga(1)-Ga(2) 101.59(19) Ga(1) Cl(1) 2.300(2) Cl(1) Ga(1) Ga(2) 104.64(6) Ga(1) Ga(2) 2.4474(11) C(32) Ga(2) Ga(1) 117.1(2) Ga(2) C(32) 2.014(7) C(21) Ga(2) Ga(1) 122.57(19) Ga(2) C(21) 2.084(7) Cl(2) Ga(2) Ga(1) 108.12(7) Ga(2) Cl(2) 2.324(2) C(12) Ga(1) C(1) 106.7(3)
C(32) Ga(2) C(21) 103.0(3)
119
Although compound 22 was not our ultimate goal, it proved that the strategy of
employing a -bonded ligand in conjunction with a carbene ancillary ligand on gallium
adequately stabilizes Ga Ga bonding. In essence, removal of the remaining chloride ligands of
22 should afford a species with a Ga=Ga double bond.
In light of the difficulties of sodium reduction, 19 was reduced with potassium metal in
toluene, which generally gave dark red to red-brown solutions in toluene. Attempts to isolate
colorful crystals, which are usually indicative of a multiply bonded species due to the low energy
gap of the * or n * transition, were inhibited by crystallization of copious amounts of
colorless carbene ligand. After a series of successive extractions with hexane/toluene (10:1),
colorless crystal formation ceased, leaving behind red oil. Placing the oil at -25 °C for several
days afforded purple-red crystals in low yield along with pale-yellow amorphous material. Single
crystal X-ray analysis of these crystals revealed a compound with a Ga6-octahedral core,
Mes4Ga6(:L)2 (23) (Fig. 2.37), containing eight triangular faces and six vertices. The balanced
chemical equation for 23 is formulated in equation 2.23.
6 MesGaCl2(:L) Mes4Ga6(:L)2 + 4 :L + 2 Mes12 K, toluene
-12 KCl
19 23
Examination of the literature reveals that there are only a few gallium clusters containing
Ga6 deltahedra subunits.251-253 It is remarkable to note that 23 is the first neutral Ga6-octahedron.
There are, however, two neutral Ga6 species worth mentioning. One of these, Cp*Ga6 (Cp* =
Me5C5),254 contains a octahedron but no metal metal bonds, thus cannot be considered a gallium
cluster, while R6Ga6 (R = -SiMe(SiMe3)2),253 which appears to have structural similarities of an
(2.23)
120
octahedron, was described by the authors as an extremely folded Ga6-chair. Further proof of its
non-octahedral Ga6 metallic core is revealed by its electron count, which only 12 skeletal
electrons are dedicated to the skeletal structure. Conversely, the 14-electron Ga6 closo skeleton
of 23 is consistent with Wade Mingos rules,112,113 supplied by eight electrons from the [MesGa]4
square planar equatorial core, while the two carbene stabilized gallium caps (Ga(:L)) can be
considered “naked” and dedicate six-electrons collectively. The only “true” Ga6-octahedron
cluster reported in the literature is the isoelectronic dianionic gallium analogue, [R6Ga6]-2 (R =
Si(CMe3)3),253 of the thoroughly studied aromatic hexaborate dianion, [B6H6]
-2.255-259
Several structural aspects of 23 are worthy of discussion. Perhaps most relevant is the
heteroleptic nature of 23, which causes subtle, yet notable, distortions within the Ga6 skeletal
framework. The slightly varied transannular Ga(1) Ga(1a), Ga(2) Ga(2a), and Ga(3) Ga(3a)
separation distances (3.65 6Å, 3.671 Å, and 3.443 Å respectively) are illustrative of this
manifestation, which ultimately affects the three fused planar quadrangle surfaces. For example,
the [MesGa]4 fragment is essentially square planar, while the two [{MesGa}2{Ga(:L)}2] planes
can best be described as Ga4-rhomboids. These slight variations cause perturbations to ideal
octahedral geometry resulting in three two-fold axes that pass through the Ga(1) Ga(1a),
Ga(2) Ga(2a), and Ga(3) Ga(3a) vectors. The Ga Ga bond distances in 23 are also interesting.
The Ga(1) Ga(2) bond distances (2.5905(11) Å), wherein a mesityl ligand is bonded to both
galliums, are longer than the Ga(1) Ga(3) and Ga(2) Ga(3), 2.5109(12) and 2.5165(12) Å,
respectively, which have carbene coordination to the Ga(3) atoms. This is contrary to the
expected trend, as the polar Ga C -bond usually results in a more + gallium atom and a net
decrease in its effective radius, and thus a shorter Ga Ga bond should be experienced.23 The
effect of carbenes on group 13 metal metal bonds is clearly not well understood.
121
There are only two structurally characterized digallanes that incorporates carbenes as a
stabilizing ligands, (L:)GaI2GaI2 (L: = :C{N(2,6-PriC6H3)CH}2) and 22, both have Ga Ga bond
distances (2.4739(12) Å and 2.4474(11) Å) that are significant shorter than that found in 23. This
Ga Ga bond lengthening in 23 may be ascribed to putative 3c-2e bonding mode which has been
used to describe the bonding arrangement in boron polyhedras.259
Some additional features of 23 are also worth mentioning. In particular, the carbene
ligands are almost parallel to one another with a small torsion angle of 11.5°, while the mesityl
ligands on the two Ga(1) atoms are C2 symmetric with a much larger torsional angle (65.23°)
with respect to one another. The mesityl ligands located on the Ga(2) atoms are highly
disordered, thus it is difficult determined their torsion angle. The Ga C bond distances in 23 are
also worthy of discussion. The Ga(1) C(1) bond distance (1.966(11) Å) is slightly longer than
the Ga(2) C(7) bond distance (1.955(11) Å), however they are comparable to that (1.957(16) Å)
in the MesGaCl2 inorganic polymer.260 As expected, the Ga(3) C(carbene) bond distance (1.982(11)
Å) is significantly longer the Ga(1) C(1) and Ga(2) C(7) distances with mesityl ligation.
Moreover, this bond distance is significantly shorter than the analogous Ga C(carbene) bond
distances of 19 (2.048(2)Å) and 22 (2.028(7) and 2.084(7) Å), which suggest that the
environment around the carbene in 23 is less crowded.
122
Figure 2.37. Molecular structure of Mes4Ga6(:L)2 (23) Table 2.24 Selected bond distances [Å] and angles [°] for Mes4Ga6(:L)2 (23)
Atoms Distance Atoms Angle Ga(1) Ga(2A) 2.5905(11) Ga(1A) Ga(2) Ga(1) 89.76(5) Ga(1) Ga(3) 2.5109(12) Ga(1A) Ga(3)-Ga(1) 93.44(5) Ga(2) Ga(3A) 2.5165(12) Ga(1A) Ga(3) Ga(2) 62.03(3) Ga(1) C(1) 1.966(11) Ga(2) Ga(3) Ga(2A) 93.68(5) Ga(2) C(7) 1.955(11) Ga(2A) Ga(1) Ga(2) 90.24(5) Ga(3) C(15) 1.982(11) Ga(3) Ga(1) Ga(3A) 86.56(5) N(1) C(15) 1.355(9) Ga(3) Ga(2) Ga(3A) 86.32(5) N(1) C(16) 1.399(9) Ga(3) Ga(1) Ga(2A) 59.09(3)
Ga(1A) Ga(2) Ga(3) 58.88(3)
123
To provide better insight into the nature of 23, computational studies at the B3LYP/6-
311+G** level were conducted on a simpler model, Ga6Ph4(:L )2 (:L =:C(HNCH)2 (23a) (Fig.
2.38), wherein the mesityl ligands are replaced with phenyl groups and the isopropyl ligands on
the carbenes are substituted with only hydrogen. The experimental and theoretical are in
reasonable agreement. However, the Ga(phenyl) Ga(phenyl) bond distances in 23a (2.643 Å) are
about 0.05 Å longer than the analogous bond distances in the experimental (2.5905 Å), while
Ga(phenyl/mes) Ga(carbene) bond distances are more comparable (23, 2.514 Å av., 23a, 2.538 Å).
Several factors may be attributed to these slight deviations such as crystal packing forces and
deviations to the ligands steric and electronic effects between the experimental and model.
Consistent with 23, however, the opposing Ga Ga bond lengths in the theoretical structure are
equivalent, thus rendering three-fold symmetry, and the Ga(phenyl) Ga(phenyl) (2.643 Å) bond
distances are longer that the Ga(phenyl) Ga(carbene) bond distances (2.537 Å av). Another interesting
feature of the model 23a is that the carbene ligands are coplanar with an effective 0° torsional
angle, perhaps the isopropyl ligands on the carbene in the experimental add steric encumbrance
and are responsible for the slight torsion observed in 23.
Natural atomic orbital (NAO) and Wiberg index (WBI) bond order analysis was also
performed on 23a as to provide better understanding of the bonding in 23. The Ga Ga bond
orders utilizing the WBI are overall smaller than those calculated using NAO bond order
analysis, while the Ga C bond orders are larger. The bond orders calculated for both methods
are shown in Table 2. 25. The Ga(carbene) Ga(phenyl) bond orders (NAO = 0.729 , 0.747; WBI =
0.606, 0.647) are larger than the Ga(phenyl) Ga(phenyl) bond orders (NAO = 0.679; WBI = 0.548).
The larger Ga(carbene) Ga(phenyl) bond order may be the result of the more electron rich Ga(:L)
fragment, which can contribute more electron density for bonding. However, all of the Ga Ga
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bond orders are less than 1.0 and can be rationalized by three-centered two-electron bonding as is
commonly accepted for main group clusters. In accordance with Wade-Mingos interpretation of
main group polyhedra, the Ga C bonds should be 2c-2e -bonds, however the Ga C bond
orders are significantly less than 1.0 (WBI 0.736; NAO 0.650). Surprisingly, the Ga C(carbene)
bond orders (WBI 0.745; NAO 0.726) are larger than the Ga C(phenyl) bond orders (WBI 0.736;
NAO 0.650), since the Ga C(carbene) is a true -bond. It is informative to note that bond orders are
commonly under estimated by these methods.
In an effort to assess aromaticity, Nucleus-Independent Chemical Shifts were computed
for 23a at the PW91PW91/6-311+G** level, and for comparison purposes, they were also
computed for the hexagallate dianion, [Ga6H6]2-. The negative NICS value (-10.2) for 23a clearly
supports aromaticity, but this value is significantly less than that of [Ga6H6]2- and [B6H6]
2- (NICS
= -27.3 and -27.521,257 respectively). This suggests that the neutrality of 23a lessens its
aromaticity. The charge on 23a, [Ga6H6]2-, and [B6H6]
2 (1.24, -0.69, and -1.78, respectively) was
calculated to compare with the respective calculated NICS values. Indeed, a correlation was
identified wherein the highly charged [B6H6]2 and [Ga6H6]
2- species are considerably more
aromatic than neutral 23a. Interestingly, although [B6H6]2 contains two and a half times the
charge of [Ga6H6]2-, its NICS value is only a marginally more negative.
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Figure 2.38 B3LYP/6-311+G** optimized geometry of Ga6Ph4(:L )2 (L : = :C(HNCH)2 (23a)
Table 2.25. Bond order for various bonds are calculated at the PW91PW91/6-31G*//B3LYP/6-311+G** for Ga6Ph4(:L )2 (:L =:C(HNCH)2 (23a) Bond Wiberg Bond Index NAO Gaaxial-Gacarbene 0.606 0.729 Gaaxial-Gabenzene 0.548 0.679 Gabenzene-Gacarbene 0.647 0.747 Ga-Ccarbene 0.745 0.726 Gaaxial-Cbenzene 0.736 0.648 Gaequatorial-Cbenzene 0.736 0.651
In conclusion, in the course of this study three new carbene adducts of mesityl group 13
dihalides, MesEX2(:L) (19, E = Ga X = Cl; 20 E = Al X = Br; 21 E = In X = Br),were isolated.
While alkali metal reduction of 20 and 21 did not provide a compound with metal metal bonds,
reductions of 19 provided a meso-digallium complex containing a Ga Ga bond, [MesGaCl(:L)]2
(22), and the unexpected formation of the first carbene stabilized Ga6 octahedron, Mes4Ga6(:L)2
126
(23). NICS calculations on the 23b signify substantial aromaticity, although somewhat less than
that of the dianionic hexagallates or hexaborates. The neutrality of 23 may reduce its aromaticity.
2.6 A New Synthetic Procedure for Arduengo’s Carbene
Arduengo’s synthesis of 1,3-di-1-adamantylimidazol-2-ylidene (Arduengo’s carbene;
AdL:), by deprotonation of 1,3-di-1-adamantylimidazolium chloride ((Ad)ImidCl) with
potassium tert-butoxide in THF, was the first report of a structurally characterized carbene.233
The report, however, provided no detailed protocol on the synthesis of starting material,
(Ad)ImidCl, nor was any single crystal X-ray data supplied for the carbene, AdL:, except for
minor structural information. Although AdL: is well known and even commercially available,
there remains no detailed protocol for its synthesis in the literature. Though a few groups have
prepared transition metal complexes stabilized by Arduengo’s carbene,261 they have cited
Arduengo’s 1999 report for the general synthesis of aryl substituted carbenes,236 which has no
specific mentioning of AdL:. This generalized protocol follows a three-step process, in which an
N-arylamine is condensed with glyoxal to give a glyoxal diimine intermediate, followed by
cyclization with chloromethyl ethyl ether to give the imidazolium salts (ImidCl). The free
carbene is generated by deprotonation of the imidazolium salts with potassium tert-butoxide.
We were interested in examining AdL: on the group 13 elements to evaluate the structure
and bonding of the carbene group 13 adducts, (AdL:)EX3, and its viability to stabilize group 13
metal metal bonds. This interest was spawned from the considerable three-dimensional steric
bulk bestowed by the adamantyl ligands and the fact that Arduengo’s carbene has been noted as
a slightly better -donor as compared to aryl carbenes.262
127
Since there was no detailed protocol of AdL: in the literature, its synthesis was pursued
by utilizing the generalized protocol cited in the Arduengo’s 1999 report. We attempted its
synthesis by reaction 1-adamantylamine (AdNH3) in n-propanol with aqueous glyoxal to give the
expected glyoxal-bis-(1-adamantyl)imine, however only a white insoluble material was isolated.
A more thorough examination of the literature revealed that a similar phenomenon was
encountered by Mol and coworkers, wherein an “white intractable precipitate formed” that could
not be adequately characterized.262
After manipulating solvents, it was found that addition of AdNH2 in toluene to aqueous
glyoxal provided glyoxal-bis-(1-adamantyl)imine (24) as a white powder in near quantitative
yields (Eq. 2.24). It is worthwhile to note that the isolation of 24 is distinctly different from the
method described by the literature report for aryldiimines. Whereas aryldiimines crash out of the
solution, only after removal of all solvent is 24 obtained as a white powder. It is reasonable that
the more aliphatic characteristics of the adamantyl ligands enhance the solubility of 24. Although
this reaction provides 24 in good yield (70-80%), adamantylamine is cost $104.00/ 25 g, thus it
was worthy to develop an alternate method to prepare 24 using 1-adamantylammonium
hydrochloride, AdNH3Cl, which is one-third the cost of adamantylamine ($145.00/100 g).
The obvious disadvantage of using AdNH3Cl is that HCl must be removed to permit the
condensation of the free amine and glyoxal, thereby lengthening the synthetic procedure by an
additional step. However, the cost advantage adequately compensated for this extra step. It was
believed that LiOH could not only neutralize HCl, but also fortuitously generate a Lewis acid,
LiCl, that would promote the condensation of the free amine with glyoxal. Thus, this reaction
was performed by reaction of AdNH3Cl in H2O with aqueous LiOH, which gave a thick white
precipitant. Addition of toluene or CHCl3 quickly dissolves the white precipitant. Glyoxal is then
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added to this solution to give 24 as an off-white powder with yields comparable with that of the
free amine synthesis (Eq. 2.24). When using CHCl3 as solvent, however, unreacted AdNH3Cl is
also isolated with the desired diimine, however separation is easily accomplished by extraction
with toluene. Crystals of 24 were acquired by slow evaporation of CHCl3/toluene. The single
crystal X-ray structure of 24 has not been reported and is shown in Figure 2.40.
H2N
N
H
H
N
ClH3N
1) LiOH/ H2O
2) glyoxal
1) glyoxal, toluene
24
Figure 2.39. Molecular structure of glyoxal-bis-(1-adamantyl)imine (24)
Consistent with Arduengo’s generalized procedure, reaction of 24 with chloromethyl
ethyl ether in THF gave the cyclized precursor, 1,3-bis-(1-adamantyl)imidazolium chloride (25),
in almost quantitative yield (Eq. 2.26). Crystals of 25 can be grown by slow evaporation of
acetone and CHCl3; however, when removed from solvent the crystals rapidly transformed into a
white amorphous material. All efforts to obtain adequate crystals for single crystal X-ray
(2.24)
129
structural analysis proved impossible. The chemical composition of 25 was confirmed by
comparing 1H NMR spectra with commercially available reference and melting point
determination.
With the imidazolium chloride precursor (25) in hand, deprotonation with potassium tert-
butoxide provided Arduengo’s carbene (26), albeit in low yield (40%) (Eq. 2.26). Crystals of 26
can be readily grown from slow evaporation of diethyl ether.
24N N
H-Cl
ClCH2OCH2CH3
THF, 2d
t-BuOK, THF
N N
Arduengo's carbene (40%)
26
25
The single crystal structure of 26 (Fig. 2.40) confirms the anticipated structure, revealing
a central planar imidazolylidene ring with adamantyl ligands situated at the nitrogen atoms.
There are a few structural features of 26 worthy of discussion. The carbenic nature of the C(1)
atom is reflected in the C(1) N(1) and C(1) N(2) bond distances (1.3624(16) and 1.3661(16) Å,
respectively), which are more than 0.1 Å shorter than the C(4) N(2) and C(14) N(1) bond
distances (1.4814(16) and 1.4841(15) Å, respectively) involving nitrogen bonding with the
(2.25)
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adamantyl ligands. The N(1) C(1) N(2) bond angle of 102.62(10)° in 26 is smaller than
expected for five membered rings (108°) and significantly smaller than the expected value for a
trigonal planar carbon. The nitrogen atoms assume a distorted trigonal planar geometry with an
average internal ring C N C bond angle of 112°.
Since the 1991 report of Arduengo’s carbene revealed little structural data on unit cell
dimensions besides its Kanvas structure, it is prudent to give some discussion in this regard.
Compound 26 crystallizes in monoclinic, space group P2(1)/c (No. 14) with the following unit
cell dimensions: a = 7.5954(5) Å, b = 19.7470(12) Å, c = 12.8016(8) Å; b = 106.5400(10)° V =
1840.6(2) Å3. A single molecule is unique to one asymmetric unit, however the unit cell contains
four molecules without any short intramolecular contacts (Fig. 2.41).
Figure 2.40. Molecular structure of Arduengo’s carbene (AdL:) (26)
Table 2.26 Selected bond distances [Å] and angles [°] for Arduengo’s carbene (AdL:) (26)
Atoms Distance Atoms Angle C(1) N(1) 1.3624(16) N(1)-C(1)-N(2) 102.62(10) C(1) N(2) 1.3661(16) C(1)-N(2)-C(4) 122.29(10) N(1)-C(14) 1.4814(16) C(1)-N(2)-C(3) 112.19(11) N(2)-C(4) 1.4841(15) C(2)-C(3)-N(2) 106.38(11)
131
Figure 2.41. A view of the unit cell of Arduengo’s carbene (AdL:) (26) showing arrangements of individual molecules To evaluate Arduengo’s carbene on group 13 metals, reaction of AdL: with GaCl3 in
diethyl ether was performed; however, instead of the anticipated 1:1 adduct, (AdL:)GaCl3, an
imidazolium gallate, [ADL:H][GaCl4] was produced (Eq. 2.27). The same conclusion was drawn
when solvent or temperature was varied. It appears that the exceptional steric bulk afforded by
the adamantyl ligands impedes the interaction of the carbenic nucleophilic center with the metal.
Indeed, studies of ligand substitution enthalpies of reactions of various carbenes on [Cp*RuCl]
showed that AdL: had the lowest reaction enthalpy and bond dissociation energies.234 The
132
authors suggested that the adamantyl groups “hinder carbene lone pair overlap with metal
orbitals”. Indeed, the adamantyl groups are quite bulky, but it has been demonstrated that
Arduengo’s carbene readily coordinates to monovalent Au(I)Cl to give adducts of (AdL:)AuCl
with a linear C Au Cl bonds angle.261 A similar phenomenon was observed when AdL: is
introduced to iodo-pentaflurobenzene, wherein a 1:1 adduct, AdL I C6HF5, is formed with a
linear C(carbene) I C(phenyl) bond angle.263 With this in mind, AdL: may be able to coordinate to
low-valent group 13 elements such as monovalent “EX” species, whereas in trivalent group 13
species the interaction between the adamantyl groups and the halides is excessively congestive
for adduct formation.
N
N
+ GaCl3
N
N
H GaCl4
In conclusion, a detailed protocol to prepare Arduengo’s carbene was established using
adamantylamine, as well as, a new, less expensive method using adamantylammonium chloride.
In these studies the crystal structure of glyoxal-bis-(1-adamantyl)imine (24) was reported, as
well as, a detailed structural report of Arduengo’s carbene. It was found that Arduengo’s carbene
may be limited to coordination to monovalent elements and may not be a choice ligand for 1:1
adduct formations with the group 13 elements.
(2.26)
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CHAPTER 3
CONCLUSION
3.1 Concluding remarks
The ultimate goal of my doctoral research was to evaluate new and established ligands
to access novel and interesting compounds containing metal metal bonds. The initial strategy of
using less bulky m-terphenyl ligands, 2,6-(4-t-BuC6H4)2C6H3- (R) and 2,6-(4-Me-C6H4)2C6H3-
(R´), with the intent to stabilize metallic rings or clusters did not produce flattering results as
only one tri-gallium catenated complex, [R3Ga3][Na3OEt3] (9), was isolated in very low yield.
These endeavors, however, were not in vain, as several new m-terphenyl-group 13 complexes
were isolated having interesting structures. Specifically, the first tris-m-terphenyl-group 13
complexes, R3In (5) and R 3In (8), were realized in these studies, as well as an m-terphenyl-oxo-
bridged dialuminum chloride complex, [RAlCl(OEt2)]2O (4) that contained exceptionally long
Al Cl bonds and a peculiar “gauche-like” arrangement of m-terphenyl ligands. These structural
features may be influenced by the anomeric effect. Computational studies may better verify this
hypothesis. Moreover, these studies of less bulky m-terphenyl ligands on group 13 metals
demonstrated that 2,6-di(4-t-butylpheny)phenyl-group 13 dihalides prefer donor solvent
coordination to give the compounds of general formula REX2(OEt2), while those of 2,6-di(4-
methylpheny)phenyl (R’) form lithium salt adducts, R’EX3Li. These differences in structure may
be the consequence of enhanced inductive effects of the tert-butyl functionality, which may
lessen the Lewis acidic behavior of the group 13 metal.
134
This study also investigated the organometallic chemistry at the group 4 group 13
interface. The first compounds (10 and 11) containing Hf group 13 bonds, Cp2Hf(ER) (E = Ga,
In; R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-), which possessed “V-shaped” E Hf E metallic cores, were
prepared. Additionally, an intriguing trimetallic fulvalene-bridged dizirconocene-gallium
complex, (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR), 12, containing rare Ga Zr bonds was
synthesized. This compound is notable as the only known complex to demonstrate gallium
engaged in bonding to two zirconium atoms. The unexpected existence of a hydride in 12
residing between the two Zr atoms was detected by 1H NMR and further supported by
computational methods.
We extended our study of less bulky m-terphenyl ligands on the group 4 metallocenes,
which yielded a trivalent titanium radical Cp2TiR (R = 2,6-(4-Me-C6H4)2C6H3-) (13) and a four-
coordinate m-terphenyl-zirconocene chloride, Cp2Zr(R)(Cl) (R = 2,6-(4-t-BuC6H4)2C6H3-) (14).
Attempts to isolate a trivalent zirconium radical, Cp2ZrR , or an m-terphenyl-titanocene chloride
Cp2Ti(R)(Cl) was inconclusive. These endeavors demonstrate that though the chemistry of group
4 metallocenes may parallel to some degree, there are distinct differences between the members
of this group.
The multidisciplinary nature of this research project extended our efforts to synthesize a
gallepin derivative. This was accomplished by a benzannulation approach, wherein 2,2 -dilithio-
Z-stilbene(TMEDA)2 (16) was allowed to react with GaCl3 to give the first gallepin,
bis(gallepin)2·TMEDA, 18. The single crystal X-ray structure of 18 revealed a complex with two
gallepin moieties bridged by a TMEDA molecule. The gallepin moieties aromatic characteristics
were confirmed by NICS calculations and suggest gallepins are less aromatic than borepins or
the tropylium ion. Furthermore, it was concluded that the phenyl substituents in 18 lessen its
135
aromatic characteristic but amine coordination has a minimal effect. Perhaps future studies will
unveil an unsupported gallepin that can provide further insight into its aromatic nature.
We also envisioned that N-heterocyclic carbenes (NHCs) could be convenient ligands to
stabilize main group metal metal bonds. Indeed, we had previously demonstrated that NHCs can
adequately stabilize neutral compounds possessing boron boron double bonds. We extended
these studies to the heavier group 13 metals by synthesizing several mesityl-group 13 carbene
adducts, (MesGaCl2(:L) (19), MesAlBr2(:L) (20), MesInBr2(:L) (21) (:L = :C{(i-Pr)NC(Me)}2),
that served as precursors to study their alkali metal reductions. While alkali metal reduction of 20
and 21 failed to give a species containing metal metal bonds, potassium graphite reduction of 19
yielded a compound with two four-coordinate gallium atoms bound through a Ga Ga bond,
[MesGaCl(:L)]2 (22). The implications of four different substituents about the gallium atoms in
22 presented a rare meso-digallane. Switching to potassium metal reduction of 19 gave the
unexpected formation of a rare Ga6 octahedron, Mes4Ga6(:L)2 (23), which is also notable as the
only neutral gallium octahedron.
Finally, a new detailed synthetic protocol to prepare Arduengo’s carbene (26) from
adamantlyammonium chloride was produced and full single crystal X-ray structural analysis was
performed. Though it was found that the adamantly ligands impedes carbene coordination to
trivalent group 13 elements, this ligand has demonstrated to readily coordinate monovalent
elements.
To conclude, the passages of this manuscript have revealed the eclectic nature of my
research project. As ideas evolved, I was encouraged to examine the chemistry and the old adage
of CHEM-IS-TRY was thoroughly practiced in the course of this project. Of course, some ideas
worked better than others; however, by having several projects the chance for success greatly
136
improved. This research group will undoubtedly be prosperous in the years to come, as the
exploration of carbenes as viable ligands to stabilize metal metal bonds has only recently
emerged.
137
CHAPTER 4
EXPERIMENTAL
4.1 General Background
4.1.1 Techniques and Reagents
Unless otherwise noted, all manipulations were conducted under anaerobic conditions
with strict exclusion of air and moisture. Standard Schlenk techniques in conjunction with an inert
atmosphere drybox (VAC He-493) were employed. Diethyl ether, hexane, and tetrahydrofuran
were distilled over sodium metal and benzophenone under a nitrogen atmosphere, while toluene
was refluxed over sodium metal. All solvents were freshly distilled and degassed prior to use.
Argon was passed through copper-based purification and molecular sieve drying columns to
ensure purity. Melting points were measured on a Haake Buchler MFB 595 802 C melting point
apparatus and are uncorrected.
1-Adamantylamine, aluminum(III) bromide, aluminum(III) chloride,
bis(cyclopentadienyl)hafnium dichloride, 2-bromobenzaldhyde, 2-bromobenzylbromide, 4-
bromotoluene, n-butyllithium, 4-tert-butylphenylbromide, 1,3-dichlorobenzene, 1,3-diisopropyl-
2-thiourea, gallium(III) chloride, glyoxal, 3-hydroxy-2-butanone, indium(III) bromide, indium(III)
chloride, iodine, lithium hydroxide, lithium nitride, magnesium fillings, 2-mesitylmagnesium
bromide, TMEDA, and triphenylphosphine were purchased from Aldrich Chemical Company
(Milwaukee, WI). Bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)zirconium
138
dichloride, potassium metal, and sodium metal were purchased from Strem, Inc (Newburyport,
MA). 1-Adamantylammonium hydrochloride and 2,4,6-triisopropylbromobenzene and were
purchased from Lancaster Synthesis (Windham, NH). Chloromethyl ethyl ether was purchased
from Tokyo Chemical Industry Company, Ltd, (Tokyo, Japan). All reagents were used as
received without further purification.
4.1.2 Instrumental Measurements
1H and 13C NMR spectra were recorded on a Varian Mercury Plus 400 MHz
spectrometer. Chemical shifts are reported in parts per million (ppm). Deuterated tetrahydrofuran
(THF-d8), benzene (C6D6), and chloroform (CDCl3) were used as the lock solvents in NMR
experiments. ESR spectra were recorded with a Bruker 300E EPR spectrometer. IR spectra were
recorded on a Nicolet-Avatar 360 FT-IR spectrometer.
X-ray Diffraction Methods
X-ray quality crystals were mounted and sealed in a glass capillary under argon. The X-
ray intensity data were measured at room temperature on a Bruker SMART APEX II X-ray
diffractometer system with graphite-monochromated Mo Ka radiation (l = 0.71073 Å) w-scan
technique. Subsequent solution and refinement was performed using the SHELXTL 6.1 solution
package operating on a Pentium computer. Data were corrected for Lorentz and polarization
effects and integrated with the manufacturer's SAINT software. Absorption corrections were
applied with the SADABS. Structures were solved by direct methods using the SHELXTL 6.1
Software Package. Non-hydrogen atomic scattering factors were taken from the literature
tabulations. Non-hydrogen atoms were located from successive difference Fourier map
calculations. In the final cycles of each refinement, the non-hydrogen atoms were refined
139
anisotropically. Hydrogen atom positions were calculated and allowed to ride on the carbon to
which they are bonded assuming a C–H bond length of 0.95 Å. Hydrogen atom temperature
factors were fixed at 1.10 times the isotropic temperature factor of the C-atom to which they are
bonded.
4.2 Preparations and Characterization of Starting Materials
4.2.1 General Syntheses of m-Terphenyl Ligands
Syntheses of m-terphenyl ligands were performed according to literature protocol.264 In
general, excess magnesium shavings were placed in a three–neck round bottom flask equipped
with stirbar, dripping funnel and condenser. The magnesium shavings were activated and covered
with a generous portion of THF. To the flask was added drop wise the arylhalide, ArX, in THF.
After complete addition, the reaction was stirred overnight and subsequently refluxed for one
hour. In another flask equipped with stirbar and dripping funnel, 1,3-dichlorobenzene covered
with a generous portion of THF was placed at -78°C. n-Butyllithium (1.6 M in hexane) was
added dropwise to this solution over a period of 1 hour. The temperature was maintained,
ensuring not to rise above -50°C. After complete addition, the reaction was stirred for an
additional hour, followed by drop wise addition of aryl Grignard reagent. This solution was
stirred overnight followed by reflux for 1 hour. The flask was cooled and iodine was added in
small portions until iodine color persisted for 30 minutes. The reaction was then quenched with
an aqueous solution of sodium sulfite until iodine color disappeared. The mother solution was
extracted with diethyl ether (3X) and water (2X). The organic portions were collected and dried
140
on rotary evaporator. The residue was crystallized in ethanol/toluene or petroleum ether. Yields
of m-terphenyliodides were generally 60-80%.
4.2.2 Lithiation of m-Terphenyl Ligands
2,6-(4-t-BuC6H4)2C6H3Li (RLi) and 2,6-(4-Me-C6H4)2C6H3Li (R Li) were prepared by
modified literature procedure.265 As a general protocol, RI of R I were dissolved in hexane and
placed at -78°C then treated with n-butyllithium and stirred overnight. The supernatant was
filtered from precipitate and all solvent removed to give air- and moisture-sensitive white to off-
white powders. General yields were 90-95%. The powders were used without further
purification. 2,6-(4-t-BuC6H4)2C6H3Li (RLi) and 2,6-(4-Me-C6H4)2C6H3Li (R Li) were
confirmed by melting point determination and 1H NMR data.
2,6-(2,4,6-i-Pr3C6H2)2C6H3Li(OEt2) was prepared by a modified literature protocol.266
2,6-(2,4,6-i-Pr3C6H2)2C6H3I was dissolved in hexane/diethyl ether (6:1) and placed at -78°C,
followed by addition of n-butyllithium (1.5 eq.) and stirred for two days. All solvent was
removed and the residue was extracted with hexane and then filtered from precipitant. The
solvent was removed in vacuo to give white powder (85%) and used without further purification.
2,6-(2,4,6-i-Pr3C6H2)2C6H3Li(OEt2) was confirmed by melting point determination and 1H NMR
data.
4.2.3 Synthesis of 2,2 -Dibromo-Z-stilbene
2,2 -Dibromo-Z-stilbene was prepared by literature protocol.218 2-Bromobenzylbromide
(100 g, 400 mmol) and triphenylphosphine (104.8 g, 400mmol) was dissolved in toluene and
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refluxed for 4 hrs. 2-bromobenzyltriphenylphosphonium bromide precipitated out of solution.
The white precipitant was filtered from solution and washed with toluene. The powder was dried
in air for 2 hrs and used in the subsequent reaction (172 g, 84%). 2-
bromobenzyltriphenylphosphonium bromide (20.11 g, 39 mmol) was dissolved in CHCl3 and
placed at 0°C. 2-Bromobenzaldhyde (7.3 g, 39 mmol) and a 50% w/v solution of sodium
hydroxide (15.6 ml, 195 mmol) was rapidly transferred to this solution and stirred vigorously for
3 hrs. The solution was extracted with water (2X) and diethyl ether (2X). The organic layers
were combined and all solvent was removed by rotary evaporation to give an oily pasty white
residue. The residue was extracted with petroleum ether and filtered from white precipitant. The
solvent was removed by rotary evaporation. This procedure was conducted two more successive
times until only and amber to yellow oil remained. 2,2 -dibromo-Z-stilbene crystallized as large
colorless crystals from the oil (9 g, 69%). Purity was determined by melting point determination
and 1H NMR data.
4.2.4 Synthesis of Bis(cyclopentadienyl)titanium(III) Chloride, [Cp2TiCl]2
Bis(cyclopentadienyl)titanium(III) chloride, [Cp2TiCl]2, was prepared from literature
protocol.183 Bis(cyclopentadienyl)titanium(IV) dichloride, Cp2TiCl2, (5 g, 20 mmol) and lithium
nitride (0.24 g, 6.6mmol) were placed in a flask and charged with THF and stirred for 16 hrs to
give a green solution. The solution was filtered from precipitant and then removed in vacuo. The
green residue was extracted with toluene and filtered from precipitant. All solvent was reduced
to give green crystalline material (2.2 g, 50%). Mp determination and 1H NMR confirmed purity.
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4.2.5 Synthesis of Mesityl-Group 13 Halides (MesEX3)
MesGaCl2,267 MesAlBr2, and MesInBr2
247 were prepared from modified literature
procedures by reaction of Mes3E (Al268, Ga269, In125) and EX3. MesMgBr (1 M solution, 50 mL,
50 mmol) in diethyl ether was added to EX3 (16.7 mmol) and stirred overnight, a thick
precipitant formed in this duration. The supernatant was filtered from precipitant and discarded.
The off-white precipitant was washed with hexane and dried in vacuo to give Mes3E as white
residues (80-85%). Mes3E was dissolved in toluene and added to EX3 in toluene and stirred
overnight, which formed a thick precipitant The reaction was refluxed for 2 hrs and allowed to
cool. The supernatant was removed and the residue washed with hexane. The powders were
dried in vacuo (60-80%) and used without further purification. Purity was confirmed by mp
determination and 1H NMR.
4.2.6 Synthesis of 1,3-Diisopropyl-4,5-dimethylimidazol-2-ylidene (:L)
1,3-Diisopropyl-4,5-dimethylimidazol-2-ylidene (:L) was synthesized from literature
protocol by potassium reduction of 1,3-diisopropyl-4,5-dimethylimidazole-2(3H)-thione. 237 1,3-
diisopropyl-2-thiourea (15.8 g, 100 mmol) and 3-hydroxy-2-butanone (8.81 g, 100 mmol) was
dissolved in 1-hexanol and refluxed for 12 h. The solvent was boil off in hood to give a thick
brown slurry. The slurry was recrystallized from hexane/hexanol. Colorless crystals of 1,3-
diisopropyl-4,5-dimethylimidazole-2(3H)-thione were washed with hexane and dried in vacuo
(12.75 g, 60%).
1,3-diisopropyl-4,5-dimethylimidazole-2(3H)-thione (12 g, 56.5 mmol) and potassium
metal (5 g, 128 mmol) was covered with THF and refluxed for 4 h. The solution was filtered
143
through celite and all solvent removed to give a off-white powder of (:L) (8.86 g, 87%). Purity
was confirmed by melting point determination and 1H NMR.
4.3 Syntheses of Less Sterically Demanding m-Terphenyl group 13 Complexes
4.3.1 Synthesis of RGaCl2(OEt2), (1) (R = 2,6-(4-t-BuC6H4)2C6H3-)
GaCl3 (1.76 g, 10 mmol) in diethyl ether (25 mL) was rapidly transferred to a yellow
slurry of (2,6-(4-t-BuC6H4)2C6H3)Li (3.47 g, 10 mmol) in diethyl ether (40 mL) at ca. -78°C and
allowed to slowly warm to r.t. After stirring for 48 hrs, a clear pale yellow solution was filtered
from white precipitant. All solvent was removed in vacuo and then the residue was extracted in
hexane/diethyl ether (1:1, 20 mL) and placed at r.t. for 2 days, which afforded colorless, cubic
crystals of 1 (2.13 g, 38% mp: 212-214°C), Elemental anal. Calc. (found) for C30H39Cl2GaO
(556.26): C, 64.78 (64.67); H, 7.07 (6.94); 1H NMR (THF-D8, 400 MHz) 1.116 (q, 6H, -
OCH2CH3); 1.360 (s, 18H, C(CH3)3); 3.385 (t, 4H, -OCH2CH3); 7.377-7.493 (m, 11H, Ar-H).
4.3.2 Synthesis of R2GaCl,(2) (R = 2,6-(4-t-BuC6H4)2C6H3-)
GaCl3 (1.22 g, 6.95 mmol) in diethyl ether (25 mL), was rapidly transferred to a yellow
slurry of (2,6-(4-t-BuC6H4)2C6H3)Li (4.85 g, 13.9 mmol) in diethyl ether (40 mL) at ca. -78°C
and allowed to slowly warm to r.t. After stirring for 12 hrs, a clear yellow solution with white
precipitant was observed. The solution was filtered from the precipitant and solvent reduced by
half. After 3 days at r.t. colorless, cubic crystals of 2 formed (2.35 g, 43%; mp: 202-204°C),
Elemental anal. Calc. (found) for C52H58GaCl (788.19): C 79.24 (79.06); H, 7.42 (7.61); 1H
NMR (THF-D8, 400 MHz) 1.31 (s, 18H, C(CH3)3); 6.987-7.267 (m, 11H, Ar-H).
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4.3.3 Synthesis of RAlBr2(OEt2), (3) (R = 2,6-(4-t-BuC6H4)2C6H3-).
AlBr3 (1.29 g, 4.8 mmol) in diethyl ether (30 mL), was rapidly transferred by cannula to a
yellow slurry of (2,6-(4-t-BuC6H4)2C6H3)Li (1.69 g, 4.8 mmol) in diethyl ether (40 mL) at ca. -
78°C and allowed to warm slowly to r.t. After stirring for 72 hrs, a colorless solution with white
precipitant was observed. The solution was filtered from precipitant and solvent reduced by a
third and then placed in freezer at -20°C. After 3 days a yellow viscous, oily residue formed. The
colorless solution was filtered from the oil and then reduced by a third and placed at r.t. for 3
days to give colorless, rectangular crystals of 3 (2.25 g, 78%; mp: 196-198°C)). Elemental anal.
Calc. (found) for C30H39AlBr2O (604.42): C 59.81 (59.64); H 6.53 (6.50); 1H NMR (D6-benzene,
400 MHz) 0.451 (t, 6H, -OCH2CH3), 1.236 (s, 18H, C(CH3)3), 3.219 (q, 4H, -OCH2CH3),
7.347-7.410 (m, 7H, Ar-H), 7.866-7.887 (m, 4H, Ar-H).
4.3.4 Synthesis of [RAlCl(OEt2)]2O (4) (R = 2,6-(4-t-BuC6H4)2C6H3-)
AlCl3 (1.34 g, 5 mmol) in diethyl ether (30 mL), was rapidly transferred by cannula to a
yellow slurry of 2,6-(4-t-BuC6H4)2C6H3)Li (3.52 g, 10 mmol) in diethyl ether (40 mL) at ca. -
78°C and allowed to warm slowly to r.t. The reaction was stirred for 48 hrs. The solution was
filtered from precipitant followed by reduction volume to ~ 20 mL then placed at r.t for 3 days.
Colorless needles of 4 formed. (1.24g, 31%, mp: 180-182 °C) 1H NMR (D6-benzene, 400 MHz)
0.52-0.55 (m, 12H, -OCH2CH3), 1.22 (s, 18H, C(CH3)3), 1.27 (s, 18H, C(CH3)3) 3.12-3.64 (m,
8H, -OCH2CH3) 7.160 (dd, 2H, Ar-H) 6.98-7.21 (m, 10H, Ar-H), 7.32-7.56 (m, 4H, Ar-H), 7.97-
8.05 (m, 6H, Ar-H).
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4.3.5. Synthesis of R3In (5) (R = 2,6-(4-t-BuC6H4)2C6H3-)
A slurry of (2,6-(4-t-BuC6H4)2C6H3)Li (1.69 g, 4.8 mmol) in diethyl ether (40 mL) was
transferred by cannula to a slurry of InCl3 (1.07 g, 4.8 mmol) in diethyl ether (30 mL) at ca. -
78°C. The reaction was slowly allowed warm to r.t. After 3 days of stirring, a clear, colorless
solution with an appreciable amount of white precipitant was observed. The solution was filtered
from precipitant and solvent reduced and placed in freezer at -20°C. After 10 days, colorless,
flat, rectangular crystals of 5 formed (0.21 g, 11.5%; mp: 288-290°C), Elemental anal. Calc.
(found) for C78H87In (1139.34): C 82.23 (82.51); H 7.70 (7.76); 1H NMR (D6-benzene, 400
MHz) 1.218 (s, 18H, C(CH3)3), 6.972-7.227 (m,11H, Ar-H).
4.3.6 Synthesis of [R´GaCl3][Li(OEt2)2] (6) (R´=2,6-(4-Me-C6H4)2C6H3-)
To a solution of GaCl3 (0.811 g, 5 mmol) in diethyl ether was added R Li (1.38g, 5
mmol) in diethyl ether (50 mL) at 0°C. The reaction was stirred overnight. All solvent was
removed in vacuo and extracted with hexane (10 mL) and filtered from precipitate. Diethyl ether
(15 mL) was added to the solution followed by removal of solvent (5mL). Upon placing the
solution at r.t., a gray oily substance formed. After several days small colorless needle shaped
crystals of 6 formed from oily residue. (1.52 g, 52%; mp: wets 98°C, 103-108°C (decomp.).)
Elemental anal. Calc. (found) for C28H37Cl3GaLiO2 (588.61): C 57.13 (54.50); H 6.34; (5.36); 1H
NMR (D6-benzene, 400 MHz) 0.58 (t, 6H, -OCH2CH3), 2.10(s, 3H, -CH3), 3.62 (t, 8H, -
OCH2CH3), 6.972-7.227 (m,11H, Ar-H).
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4.3.7 Synthesis of [R´InCl3][Li(OEt2)(THF)] (7) (R´=2,6-(4-Me-C6H4)2C6H3-)
A slurry of 2,6-(4-Me-C6H4)2C6H3Li (10 mmol, 1.89 g) in diethyl ether (30 mL) was
transferred slowly via cannula to a solution of InCl3 (2.21g, 10mmol) in THF (25 mL) at 0°C and
stirred for 24hrs. All solvent was removed and extracted with diethyl ether (25 mL) and hexanes
(20 mL). Colorless crystals of 7 formed over several days (2.52 g, 40%; mp: wets 135-137 °C)
1H NMR (D6- Benzene, 400 MHz) 0.58 (t, 6H, -OCH2CH3), 2.10(s, 3H, CH3), 3.62 (t, 8H, -
OCH2CH3), 6.972-7.227 (m,11H, Ar-H).
4.3.8 Synthesis of R´3In (8) (R´= 2,6-(4-Me-C6H4)2C6H3-)
A slurry of 2,6-(4-Me-C6H4)2C6H3Li (10 mmol, 1.89 g) in diethyl ether (50mL) and
toluene (10 ml) was transferred slowly via cannula to a solution of InCl3 (2.21g, 10 mmol) in
toluene (25 mL) at -78°C. The reaction was allowed to warm to room temperature and stirred
overnight for ~18 hr. The solution was filtered from the white precipitant then all solvent was
removed. The creamy residue was extracted in diethyl ether (15 mL) and hexane (20 mL),
wherein an oily residue formed at the bottom of the flask. The solution was filtered from the oily
residue and placed at room temperature overnight, resulting in large, cubic, colorless crystals of
8. (1.03 g, 68%); mp 239-240°C., Anal.: Calc. (Found) for C60H51In (886.86): C 81.25 (81.07); H
5.80 (5.79). 1H NMR (D6-Benzene, 400 MHz) 2.10(s, 6H, CH3), 6.82-6.85(m, 8H, Ar´-H), 7.00
(dd, 1H, p-C6H3) 7.78 (d, 2H, m-C6H3).
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4.4 Syntheses of Organometallic Group 13 Group 4 Complexes
4.4.1 Synthesis of Cp2Hf(GaR)2, (10) (R = 2,6-(2,4,6-i-Pr3C6H2)2C6H3-)
RGaCl2 (2.00 g, 4.00 mmol) and Cp2HfCl2 (1.52 g, 4.00 mmol) and finely divided sodium
metal (0.500 g, 22.0 mmol) were placed in a flask and charged with diethyl ether (80 mL). The
resultant slurry was stirred for three days. The solution was filtered from the precipitant and
reduced in volume by 50%. Upon standing at -25°C for 3 days, small green-black crystals of 10
were obtained. (1.83 g, 33%. m.p. 274 °C. Anal. Calc. for C86H118OGa2Hf: C, 69.05; H, 7.82%.
Found: C, 69.48; H 8.17%. 1H NMR (D6-benzene C6D6): ppm 1.29 (d, 24H, o-CH(CH3)2), 1.35
(d, 24H, o-CH(CH3)2), 1.51 (d, 24H, p-CH(CH3)2), 2.98 (sept, 4H, p-CH(CH3)2), 3.26 (sept, 8H,
o-CH(CH3)2), 3.87 (s, 10H, C5H5), 7.21 (s, 6H, -C6H3), 7.26 (s, 8H, -C6H2).
4.4.2 Synthesis of Cp2Hf(GaR)2, (11) (R =2,6-(2,4,6-i-Pr3C6H2)2C6H3-)
RInCl2 (2.40 g, 3.75mmol) and Cp2HfCl2 (1.42 g, 3.75 mmol) and finely divided sodium
metal (0.500 g, 22.0 mmol) were placed in a flask and charged with diethyl ether (80 mL). The
resultant slurry was stirred for three days. The solution was filtered from the precipitant and
reduced in volume by 50%. Upon standing at -25°C for 3 days, dark purple crystals of 11
formed. (1.24 g, 21%. m.p. 174°C (wets) 284°C (decomp.) Anal. Calc. for C86H118OIn2Hf: C,
64.99; H, 7.36%. Found: C, 65.53; H, 7.72 %. 1H NMR (C6D6): ppm 1.29 (d, 24H, o-
CH(CH3)2), 1.35 (d, 24H, o-CH(CH3)2), 1.51 (d, 24H, p- CH(CH3)2), 2.96 (sept, 4H, p-
CH(CH3)2), 3.26 (sept, 8H, o-CH(CH3)2), 3.96 (s, 10H, C5H5), 7.21 (s, 6H, -C6H3), 7.25 (s, 8H, -
C6H2).
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4.4.3 Synthesis of (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR), (12) (R = 2,6-(4-t-BuC6H4)2C6H3-)
RGaCl2·(OEt2) (5.54 g, 10 mmol) in diethyl ether (75 mL) was transferred to a flask
containing Cp2ZrCl2 (2.92 g, 10 mmol) and finely divided sodium metal (1 g, 43.5 mmol) and
stirred at room temperature. The initial colorless solution turned brown after 24 hours. After 5
days, a reddish brown solution was filtered from precipitant. The filtrate was collected and
solvent removed in vacuo, resulting in a brownish-black residue. The residue was extracted with
toluene (15 mL), and the solution was filtered at ca. -78 °C. The solution was placed at 5°C,
where upon overnight purple-black crystals formed. The crystals were re-crystallized in a
mixture of toluene and diethyl ether (1:1 ratio, 20 mL total). After 2 weeks at room temperature,
purple-black, flat, rectangular X-ray quality crystals of 12 formed (0.615 g, 0.627 mmol, 6.3 %
yield). m.p. 253-255°C, Elemental anal. (Complete Analysis Laboratories, Inc., Parsippany, NJ)
Calc.(found) for C53H56ClGaZr2 (980.64): C, 64.91(64.75); H, 5.76 (5.33).; 1H NMR (400 MHz,
[D8]THF): = 7.46 - 7.56 (m, 11H, Ar-H), 7.14 - 7.26 (m, 5H, C6H5CH3), 5.26 (s, 5H, C5H5),
5.12 (s, 5H, C5H5); 5.91, 5.62, 4.26, 4.20, 3.85, 3.79, 3.70, 3.53 (m, 1H x 8, two ABCD spin
systems, C10H8), 2.30 (s, 3H, C6H5CH3), 1.29 (s, 18H, C(CH3)3), 4.316 (s, 1H, Zr-H-Zr); IR
(KBr): = 3114.83 (w), 3044.64 (w), 2960.68 (s), 2902.51 (w), 2864.98 (w), 1529.43 (m),
1507.98 (m), 1461.08 (m), 1438.41 (m), 1393.85 (m), 1362.21 (m), 1289.88 (m), 1115.86 (m),
1042.00 (s), 1014.85 (s), 797.20 (vs), 729.69 (s), 693.98 (m), 574.88 (w).
4.5 Syntheses of m-Terphenyl Group 4 Metallocenes
4.5.1 Synthesis of Cp2TiR´ (R´ = 2,6-(4-Me-C6H4)2C6H3) (13)
R´Li (1.25 g, 4.7 mmol) in THF (25 mL) was slowly added to [Cp2TiCl]2 (1.0 g, 4.7
mmol) in THF (25 mL) at ca. -78°C. The reaction was allowed to warm to room temperature and
149
stirred overnight. All solvent was removed in vacuo, and the residue was extracted with toluene
(25 mL). The toluene solution was removed in vacuo, and the residue was extracted with diethyl
ether (25 mL). The solution was filtered and reduced by half then placed in a -25°C freezer.
Overnight green-brown needles of 13 were isolated (1.03 g, 50%), mp. 180-182°C. Anal.: Calc.
(Found) for C30H27Ti (435.40): C, 82.76 (82.93); H, 6.25 (6.27).
4.5.2 Synthesis of Cp2ZrR(Cl) (R = 2,6-(4-t-Bu-C6H4)2C6H3) (14)
RLi (0.265 g, 1 mmol) in toluene (10 mL) was added to a toluene (5 mL) solution of
Cp2ZrCl2 (0.292g, 1 mmol) at -78°C. Upon addition, the pale creamy solution of Cp2ZrCl2 turned
pale yellow. The solution was allowed to warm to room temperature and stirred overnight. The
yellow solution was reduced in vacuo to ~ 5mL and placed at room temperature. Colorless,
needle-like crystals of 14 formed overnight. (0.52 g, 87%) mp. 221-222°C. Anal.: Calc. (Found)
for C43H47ClZr (690.51): C, 74.79 (73.72); H, 6.86 (6.70).1H NMR (D6-Benzene, 400 MHz)
1.06 (s, 9H, -C(CH3)3) 1.15 (s, 9H, -C(CH3)3), 1.99 (s, 3H, Toluene -CH3), 5.65, (s, 10H, -C5H5),
6.85-6.90 (m, 5H, toluene Ar H), 6.95-7.21 (m, 10H, Ar H).
4.6 Synthesis of Gallepins and Dilithium Precursor
4.6.1 Synthesis of 2,2 -Dilithio-Z-stilbene(TMEDA)2 (16)
2,2-Dibromo-Z-stilbene(13) (1.69g, 5 mmol) was dissolved in diethyl ether (50 mL) and
treated with of n-butyllithium (6.25 mL, 1.6 M, 10 mmol) at -78°C. The solution was stirred
overnight resulting in a yellow solution. All solvent was removed in vacuo, and the residue was
extracted with hexane (30 mL). Upon addition of hexane a white precipitant crashed out of
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solution (LiBr) and a brown-orange solution formed. The solution was filtered from the
precipitant and treated with 1.1 mL TMEDA. The solution was reduced by half and placed at -
25°C. Orange-red crystals formed overnight. Procedure B: 2,2-Dibromo-Z-stilbene(13) (1.69g, 5
mmol) was dissolved in hexane (50 mL) and treated with of n-butyllithium (6.25 mL, 1.6 M, 10
mmol) at -78°C. The solution was stirred overnight resulting in a yellow solution and a thick
orange precipitant. All solvent was removed by filter cannula to give a orange powder. Diethyl
ether (10 mL) and hexane (50 mL) was added followed by addition of TMEDA. The solution
was reduced by half and placed at -25°C. Orange-red crystals of 16 formed overnight (0.72 g, 34
%) m.p. 45-46°C, Found (calc.) for C26H42Li2N4 C: 73.38 (73.56) H: 10.01 (9.97) N: 13.22
(13.20) 1H NMR 1.281 (broad s, 8H, CH2N), 1.625 (broad s, 24H, N(CH3)2) 6.748 (d, 2H,=CH)
7.207- 7.227 (m, 2H, ArH) 7.326-7.367 (m, 2H, ArH) 7.423-7.441(m, 2H, ArH) 8.244-8.264 (m,
2H, ArH).
4.6.2 Synthesis of [spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)], (17)
2,2- dibromo-Z-stilbene (1.69g, 5 mmol) (16) was dissolved in diethyl ether (50 mL )and
treated with of n-butyllithium (6.25 mL,1.6 M, 10 mmol) at -78°C. The solution was stirred
overnight resulting in a yellow solution. All of the solvent was removed in vacuo, and the
residue was extracted with hexane (30 mL) and filtered from precipitant. The resulting orange
solution was placed at 0°C and transferred to GaCl3 (0.88g, 5 mmol) in 20 mL of diethyl ether.
The reaction was allowed to proceed overnight (~16 hrs). The mother solution was removed and
the residue extracted with 25 mL of toluene. The solvent was reduced to ~10 mL and placed at -
25 °C. Colorless crystals of 17 formed after three days.
151
4.6.3 Synthesis of bis(gallepin) TMEDA (18)
16 (0.70 g, 1.65 mmol) was dissolved in diethyl ether (40 mL) and added to GaCl3 (0.29
g, 1.65 mmol) in diethyl ether (25 mL) at ca. -78°C, and stirred for 5 hours. The dry ice bath was
removed and the reaction was allowed continued stirring for 12 hours. An appreciable amount of
precipitant was observed during this time. The supernatant was filtered from precipitant,
followed by reduction of solvent (in vacuo) to ~ 10 mL. Small colorless crystal formed
immediately, which were re-dissolved by light heating. The solution was placed in a -25°C
freezer, where overnight large colorless crystals of 18 formed (0.44 g). The remaining precipitant
was taken up in toluene (20 mL) and solvent reduced by half to yield additional crystals (0.34g).
Yield: (0.78 g, 69%) mp wets 207 °C, complete decomposition 248°C, (Found: C, 59.76; H,
5.28; N, 4.27. Calc. for C34H36Cl2Ga2N2: C, 59.79; H, 5.31; N, 4.10); 1H NMR H (DMSO-d6,
400 MHz) 2.31 (12H, s, -N(CH3)2), 2.58 (4H, s, NCH2), 6.62-6.73 (4H, m, =CH), 7.19-7.42
(12H, m, ArH), 7.70-7.78 (4H, m, ArH).
4.7 Synthesis Carbene Group 13 complexes
4.7.1 Synthesis of MesGaCl2(:L) (19), MesAlBr2(:L) (20), and MesInBr2(:L) (21)
Compounds 19, 20, and 21 were prepared in similar manner by reaction of :L and
MesEX2. In general, :L (3.9 g, 15 mmol) in toluene (50 mL) was transferred to MesEX2 (2.7g 15
mmol) in diethyl ether. For 19 and 20, the clear colorless solution gradually became cloudy and
after 18hr a heavy precipitant formed, whereas for 21 a yellow solution formed. Removal of all
volatiles in vacuo gives off-white powder, which were dissolved in tetrahydrofuran/methylene
dichloride. Removal of solvent until incipient crystallization afforded large colorless crystals
overnight (91% av.) 19 (mp 177°C, 1H NMR (CDCl3) 1.41 (d, 12H, NCH(CH3)2) 2.23 (s, 3H,
152
p-CH3), 2.28 (s, 6H, [imidazoleC(CH3)]2) 2.48 (s, 6H, o-CH3), 5.52 (sept, 2H, NCH(CH3)2), 6.78 (s,
2H, Ar H); 20 (mp 187°C . 1H NMR (CDCl3) 1.38 (d, 12H, NCH(CH3)2) 2.21 (s, 3H, p-CH3),
2.27 (s, 6H, [imidazoleC(CH3)]2) 2.51 (s, 6H, o-CH3), 5.58 (sept, 2H, NCH(CH3)2), 6.73 (s, 2H,
Ar H); 21(mp 149-150, 1H NMR (C6D6) 1.07, (d, 24H, NCH(CH3)2), 1.50 (s, 6H,
[imidazoleC(CH3)]2), 1.52 (s, 6H, [imidazoleC(CH3)]2), 2.19 (s, 3H, p-CH3), 2.78 (s, 6H, o-CH3), 5.33-
5.52 (m, 4H, NCH(CH3)2), 6.84 (s, 2H, Ar H).
4.7.2 Synthesis of [MesGaCl(:L)]2 (22)
Compound 19 (3.78 g, 7.2 mmol) and potassium graphite, KC8, (3.0 g, 22 mmol) in
diethyl ether were stirred for three days at r.t. The solution was filtered and solvent was removed
in vacuo resulting in a yellow residue. The residue was extracted with hexanes and filtered. The
solvent was reduced to ~2 mL giving a yellow oily residue and placed -25°C where small pale-
yellow crystals formed over several days. (0.3 g, 9 %, mp (decomp) 94-96°C) 1H NMR (benzene-
d6) 1.03 (d, 24H, NCH(CH3)2), 1.52 (s, 12H, [C(CH3)im]2), 2.32 (s, 6H, p-CH3), 2.82 (s, 12H,
o-CH3) s, 5.79 (m, 4H, NCH(CH3)2), 6.92 (s, 4H, Ar H)
4.7.3 Synthesis of Mes4Ga6(:L)2 (23)
Compound 19 (3.00 g, 6.8 mmol) and potassium, (0.54 g, 13.6 mmol) in toluene were
heated until potassium melted and stirred for three days at r.t. The mother solution was filtered
from precipitant followed by reduction of solvent to ~2 mL and addition of hexane (1mL). The
solution was placed at -25°C, wherein pale-yellow amorphous material along with small cubic
purple-red crystals formed over a period of weeks. (~0.1 g, 6%, mp. 148°C) 1H NMR (benzene-
d6) 1.05 (d, 24H, NCH(CH3)2), 1.18 (s, 12H, C(CH3)im), 2.32 (s, 24H, p-CH3) 2.82 (s, 24H, o-
CH3), 5.78 (sept, 4H, NCH(CH3)2), 6.92 (s, 8H, Ar H)
153
4.8 Synthesis of Arduengo’s Carbene
4.8.1 Synthesis of glyoxal-bis-(1-adamantyl)imine (24)
Adamantylammonium chloride (29.9 g, 159 mmol) dissolved in H2O (250 mL) was
stirred until dissolved and treated with LiOH (3.66 g, 159 mmol) in H2O (100 mL). Upon
addition of LiOH solution a white precipitant formed immediately. Complete addition of LiOH
results in a thick white slurry. The reaction was stirred for 1 hr, where subsequent addition of
toluene results in two layers and disappearance of white slurry. Stirring was continued for an
additional hour. An aqueous 40% glyoxal solution (11.5 mL, 79.5 mmol) was then added and
stirred for ~15 hrs. The two layers were separated. The aqueous layer was extracted (2X) with
toluene. The organic layers were combined and solvent remove in vacuo. The beige solid was
crystallized in toluene, filtered and dried, resulting in 24 as white crystalline material. (18.5 g,
72%, m.p. 243.5-244°C) 1H NMR (CDCl3): 1.64-1.78 (m, 24 H), 2.15 (s, 6H) 7.83, (s, 2H).
13C NMR (CDCl3) 29.5, 36.6, 42.9, 58.7, 158.0.
4.8.2 Synthesis of 1,3-bis-(1-adamantyl)imidazolium chloride (25)
To 24 (15 g, 46.2 mmol) in THF, chloromethyl ethyl ether (4.5 g, 47.6 mmol) was added
dropwise by syringe. After 1 hour precipitant formed, and the color of the solution changed from
yellow to orange. The reaction was allowed continued stirring for 18hrs then placed at -20°C.
The precipitant was filtered and washed with THF and hexanes and dried. The powder was
dissolved in CHCl3, and then precipitated with THF (10 g, 58%, 335°C). 1H NMR (CDCl3):
1.76 (m, 12H) 2.29 (s, 18 H), 7.54 (s, 2H) 10.39 (s, 1H).
154
4.8.3 Synthesis of 1,3-bis-(1-adamantyl)imidazol-2-ylidene “Arduengo’s carbene” (26)
In drybox, 25 (10 g, 26 mmol) was covered with THF and rapidly stirred. Potassium tert-
butoxide (3 g, 26 mmol) was added in small portions and stirred overnight. All solvent was
removed and residue extracted with toluene then filtered through a celite column. All solvent
was removed and the residue was taken up in diethyl ether. Removal of solvent until incipient
precipitation and setting at r.t. for one day gave colorless crystal of 26. (3.5 g, 40%) Melting
point (240-241°C) and NMR data (1.58 (s, 12H), 2.01 (s, 6H), 2.29 (s, 12H) 6.91(s,2H)
compares well with reference.
155
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172
APPENDIX A
CRYSTALLOGRAPHIC DATA
Structural Data for RGaCl2(OEt2) (1) (R = 2,6-(4-t-BuC6H4)2C6H3-)
Table 1. Crystal data and structural refinement for RGaCl2(OEt2) (1)
Empirical formula C42H39Cl2GaO Formula weight 556.23 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Orthorhombic, Pna2(1) Unit cell dimensions a = 24.640(7) Å b = 11.365(3) Å c = 21.545(6) Å
= 90°
= 90°
= 90°
Volume 6033(3) Å3 Z, Calculated density 8, 1.225 Mg/m3 Absorption coefficient 1.108 mm-1 F(000) 2336 Crystal size 0.40 x 0.35 x 0.30 mm Theta range for data collection 1.89 to 25.00 deg. Limiting indices -29<=h<=29, -13<=k<=12, -24<=l<=25 Reflections collected / unique 35166 / 10454 [R(int) = 0.0313] Completeness to theta = 25.00 99.8 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7322 and 0.6655 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 10454 / 1 / 608 Goodness-of-fit on F^2 1.042 Final R indices [I>2sigma(I)] R1 = 0.0463, wR2 = 0.1124 R indices (all data) R1 = 0.0593, wR2 = 0.1189 Absolute structure parameter 0.286(11) Largest diff. peak and hole 0.416 and -0.213 e.Å-3
173
Table 2. Bond Lengths [Å] for RGaCl2(OEt2) (1) Atoms Distance Atom Distance Ga(1)-C(1) 1.985(5) C(21)-C(22) 1.378(7) Ga(1)-O(1) 2.041(4) C(23)-C(25) 1.526(8) Ga(1)-Cl(1) 2.1872(13) C(23)-C(26) 1.495(11) Ga(1)-Cl(2) 2.2238(14) C(23)-C(24) 1.552(11) Ga(2)-C(31) 1.984(4) C(27)-C(28) 1.306(11) Ga(2)-O(2) 2.032(4) C(29)-C(30) 1.428(14) Ga(2)-Cl(3) 2.1993(15) C(31)-C(32) 1.392(7) Ga(2)-Cl(4) 2.2004(14) C(31)-C(36) 1.417(6) O(1)-C(27) 1.423(9) C(32)-C(33) 1.407(7) O(1)-C(29) 1.448(7) C(32)-C(37) 1.502(6) O(2)-C(57) 1.488(10) C(33)-C(34) 1.386(7) O(2)-C(59) 1.486(11) C(34)-C(35) 1.378(8) C(1)-C(2) 1.402(6) C(35)-C(36) 1.407(7) C(1)-C(6) 1.426(6) C(36)-C(47) 1.492(7) C(2)-C(3) 1.404(6) C(37)-C(42) 1.382(6) C(2)-C(7) 1.510(6) C(37)-C(38) 1.391(6) C(3)-C(4) 1.367(7) C(38)-C(39) 1.400(7) C(4)-C(5) 1.392(7) C(39)-C(40) 1.379(7) C(5)-C(6) 1.379(7) C(40)-C(41) 1.385(6) C(6)-C(17) 1.485(6) C(40)-C(43) 1.548(7) C(7)-C(8) 1.370(6) C(41)-C(42) 1.386(6) C(7)-C(12) 1.393(6) C(43)-C(46) 1.523(8) C(8)-C(9) 1.393(6) C(43)-C(45) 1.531(8) C(9)-C(10) 1.398(6) C(43)-C(44) 1.536(8) C(10)-C(11) 1.372(7) C(47)-C(48) 1.376(6) C(10)-C(13) 1.522(7) C(47)-C(52) 1.406(6) C(11)-C(12) 1.381(7) C(48)-C(49) 1.389(7) C(13)-C(15) 1.443(10) C(49)-C(50) 1.378(7) C(13)-C(14) 1.482(11) C(50)-C(51) 1.403(7) C(13)-C(16) 1.526(9) C(50)-C(53) 1.539(8) C(17)-C(22) 1.384(6) C(51)-C(52) 1.364(7) C(17)-C(18) 1.411(6) C(53)-C(55) 1.492(9 C(18)-C(19) 1.369(7) C(53)-C(56) 1.523(9) C(19)-C(20) 1.385(7) C(53)-C(54) 1.577(9) C(20)-C(21) 1.401(7) C(57)-C(58) 1.311(14) C(20)-C(23) 1.532(8) C(59)-C(60) 1.46(2)
174
Table 3. Bond angles [°] for RGaCl2(OEt2) (1) Atoms Angle Atoms Angle C(1)-Ga(1)-O(1) 105.89(15) C(10)-C(13)-C(14) 108.0(5) C(1)-Ga(1)-Cl(1) 123.49(12) C(15)-C(13)-C(16) 107.5(8) O(1)-Ga(1)-Cl(1) 101.47(11) C(10)-C(13)-C(16) 112.6(5) C(1)-Ga(1)-Cl(2) 118.72(13) C(14)-C(13)-C(16) 103.4(8) O(1)-Ga(1)-Cl(2) 95.05(11) C(22)-C(17)-C(18) 116.5(4) Cl(1)-Ga(1)-Cl(2) 106.70(6) C(22)-C(17)-C(6) 122.7(4) C(31)-Ga(2)-O(2) 104.01(16) C(18)-C(17)-C(6) 120.8(4) C(31)-Ga(2)-Cl(3) 123.84(13) C(19)-C(18)-C(17) 120.9(4) O(2)-Ga(2)-Cl(3) 102.93(14) C(18)-C(19)-C(20) 123.1(5) C(31)-Ga(2)-Cl(4) 118.80(13) C(21)-C(20)-C(19) 115.8(5) O(2)-Ga(2)-Cl(4) 94.99(11) C(21)-C(20)-C(23) 122.6(5) Cl(3)-Ga(2)-Cl(4) 106.67(7) C(19)-C(20)-C(23) 121.6(5) C(27)-O(1)-C(29) 116.2(5) C(22)-C(21)-C(20) 121.9(4) C(27)-O(1)-Ga(1) 124.5(4) C(17)-C(22)-C(21) 121.9(4) C(29)-O(1)-Ga(1) 117.0(4) C(20)-C(23)-C(25) 113.8(5) C(57)-O(2)-C(59) 119.8(7) C(20)-C(23)-C(26) 110.0(6) C(57)-O(2)-Ga(2) 114.4(4) C(25)-C(23)-C(26) 108.9(6) C(59)-O(2)-Ga(2) 122.7(6) C(20)-C(23)-C(24) 108.8(5) C(2)-C(1)-C(6) 118.4(4) C(25)-C(23)-C(24) 107.1(6) C(2)-C(1)-Ga(1) 123.4(3) C(26)-C(23)-C(24) 108.0(8) C(6)-C(1)-Ga(1) 117.6(3) C(28)-C(27)-O(1) 127.2(10) C(1)-C(2)-C(3) 119.5(4) C(30)-C(29)-O(1) 115.1(9) C(1)-C(2)-C(7) 124.0(4) C(32)-C(31)-C(36) 119.3(4) C(3)-C(2)-C(7) 116.5(4) C(32)-C(31)-Ga(2) 117.6(3) C(4)-C(3)-C(2) 121.2(5) C(36)-C(31)-Ga(2) 122.2(3) C(3)-C(4)-C(5) 120.0(5) C(31)-C(32)-C(33) 120.3(4) C(6)-C(5)-C(4) 120.4(5) C(31)-C(32)-C(37) 121.2(4) C(5)-C(6)-C(1) 120.2(4) C(33)-C(32)-C(37) 118.5(4) C(5)-C(6)-C(17) 118.6(4) C(34)-C(33)-C(32) 120.0(5) C(1)-C(6)-C(17) 121.2(4) C(35)-C(34)-C(33) 120.3(5) C(8)-C(7)-C(12) 117.3(4) C(34)-C(35)-C(36) 120.7(5) C(8)-C(7)-C(2) 121.5(4) C(35)-C(36)-C(31) 119.2(4) C(12)-C(7)-C(2) 121.0(4) C(35)-C(36)-C(47) 117.8(4) C(7)-C(8)-C(9) 120.7(4) C(31)-C(36)-C(47) 123.0(4) C(10)-C(9)-C(8) 122.3(4) C(42)-C(37)-C(38) 118.2(4) C(11)-C(10)-C(9) 116.0(4) C(42)-C(37)-C(32) 121.5(4) C(11)-C(10)-C(13) 123.0(5) C(38)-C(37)-C(32) 120.3(4) C(9)-C(10)-C(13) 121.0(5) C(37)-C(38)-C(39) 120.1(4) C(10)-C(11)-C(12) 122.2(4) C(40)-C(39)-C(38) 122.0(4) C(11)-C(12)-C(7) 121.5(4) C(39)-C(40)-C(41) 116.6(4)
175
Table 3 (con’t). Bond angles [°] for RGaCl2(OEt2) (1) Atoms Angle Atoms Angle C(15)-C(13)-C(10) 113.4(5) C(39)-C(40)-C(43) 120.0(4) C(15)-C(13)-C(14) 111.6(10) C(41)-C(40)-C(43) 123.4(4) C(40)-C(41)-C(42) 122.4(4) C(49)-C(50)-C(51) 116.4(5) C(37)-C(42)-C(41) 120.5(4) C(49)-C(50)-C(53) 120.7(5) C(46)-C(43)-C(45) 107.9(6) C(51)-C(50)-C(53) 122.8(5) C(46)-C(43)-C(44) 107.5(6) C(52)-C(51)-C(50) 121.0(4) C(45)-C(43)-C(44) 110.0(6) C(51)-C(52)-C(47) 122.5(4) C(46)-C(43)-C(40) 108.9(5) C(55)-C(53)-C(50) 110.1(5) C(45)-C(43)-C(40) 110.5(5) C(55)-C(53)-C(56) 112.1(6) C(44)-C(43)-C(40) 111.8(4) C(50)-C(53)-C(56) 112.9(5) C(48)-C(47)-C(52) 116.4(4) C(55)-C(53)-C(54) 107.9(6) C(48)-C(47)-C(36) 121.4(4) C(50)-C(53)-C(54) 108.0(5) C(52)-C(47)-C(36) 122.0(4) C(56)-C(53)-C(54) 105.5(6) C(47)-C(48)-C(49) 121.0(4) C(58)-C(57)-O(2) 122.0(11) C(50)-C(49)-C(48) 122.6(5) C(60)-C(59)-O(2) 109.1(13)
176
Structural Data for R2GaCl (2) (R = 2,6-(4-t-BuC6H4)2C6H3-)
Table 4. Crystal data and structural refinement for R2GaCl (2) Empirical formula C52H58ClGa Formula weight 788.15 Temperature 273(2) K Wavelength 0.71073 A Crystal system, space group Monoclinic, P2(1)/n Unit cell dimensions a = 17.587(4) Å b = 13.911(3) Å c = 19.968(4) Å
= 90°
= 110.010(4)°
= 90°
Volume 4590.4(16) Å3 Z, Calculated density 4, 1.140 Mg/m3 Absorption coefficient 0.689 mm-1 F(000) 1672 Crystal size 0.35 x 0.25 x 0.15 mm Theta range for data collection 1.82 to 25.00 deg. Limiting indices -20<=h<=20, -14<=k<=16, -23<=l<=23 Reflections collected / unique 27144 / 8018 [R(int) = 0.0281] Completeness to theta = 25.00 99.2 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 8018 / 0 / 487 Goodness-of-fit on F^2 1.019 Final R indices [I>2sigma(I)] R1 = 0.0472, wR2 = 0.1284 R indices (all data) R1 = 0.0678, wR2 = 0.1422 Largest diff. peak and hole 0.789 and -0.188 e.Å-3
177
Table 5. Bond Lengths [Å] for R2GaCl (2) Atoms Distances Atoms Distances Ga(1)-C(1) 1.981(3) C(20)-C(23) 1.530(5)
Ga(1)-C(27) 1.997(3) C(21)-C(22) 1.384(4)
Ga(1)-Cl(1) 2.2537(10) C(23)-C(26) 1.511(7)
C(1)-C(6) 1.405(4) C(23)-C(24) 1.512(6)
C(1)-C(2) 1.411(4) C(23)-C(25) 1.519(8)
C(2)-C(3) 1.402(4) C(27)-C(32) 1.404(4)
C(2)-C(7) 1.485(4) C(27)-C(28) 1.421(4)
C(3)-C(4) 1.373(4) C(28)-C(29) 1.402(5)
C(4)-C(5) 1.378(4) C(28)-C(33) 1.478(5)
C(5)-C(6) 1.395(4) C(29)-C(30) 1.383(6)
C(6)-C(17) 1.489(4) C(30)-C(31) 1.364(6)
C(7)-C(12) 1.389(4) C(31)-C(32) 1.400(5)
C(7)-C(8) 1.392(4) C(32)-C(43) 1.492(4)
C(8)-C(9) 1.384(4) C(33)-C(34) 1.391(5)
C(9)-C(10) 1.392(4) C(39)-C(42) 1.538(6)
C(10)-C(11) 1.396(4) C(39)-C(40) 1.547(7)
C(10)-C(13) 1.528(4) C(39)-C(41) 1.532(6) C(10)-C(13) 1.528(4) C(43)-C(44) 1.398(4) C(11)-C(12) 1.387(4) C(43)-C(48) 1.392(4) C(13)-C(15) 1.482(6) C(44)-C(45) 1.376(4) C(13)-C(14) 1.510(7) C(45)-C(46) 1.393(4) C(13)-C(16) 1.527(6) C(46)-C(47) 1.401(4) C(17)-C(22) 1.385(4) C(46)-C(49) 1.533(4) C(17)-C(18) 1.397(4) C(47)-C(48) 1.369(4) C(18)-C(19) 1.381(4) C(49)-C(50) 1.520(4) C(19)-C(20) 1.390(5) C(49)-C(51) 1.536(5) C(20)-C(21) 1.396(4) C(49)-C(52) 1.543(5)
178
Table 6. Bond angles [°] for R2GaCl (2) Atoms Angle Atoms Angle C(1)-Ga(1)-C(27) 137.37(12) C(26)-C(23)-C(25) 110.9(6) C(1)-Ga(1)-Cl(1) 106.69(9) C(24)-C(23)-C(25) 107.6(5) C(27)-Ga(1)-Cl(1) 115.76(9) C(32)-C(27)-C(28) 118.9(3) C(6)-C(1)-C(2) 118.5(3) C(32)-C(27)-Ga(1) 120.5(2) C(6)-C(1)-Ga(1) 117.12(19) C(28)-C(27)-Ga(1) 119.9(2) C(2)-C(1)-Ga(1) 124.4(2) C(29)-C(28)-C(27) 119.4(3) C(1)-C(2)-C(3) 119.6(3) C(29)-C(28)-C(33) 119.0(3) C(1)-C(2)-C(7) 121.7(2) C(27)-C(28)-C(33) 121.5(3) C(3)-C(2)-C(7) 118.7(2) C(30)-C(29)-C(28) 120.7(3) C(4)-C(3)-C(2) 120.9(3) C(31)-C(30)-C(29) 119.7(3) C(3)-C(4)-C(5) 120.1(3) C(30)-C(31)-C(32) 121.9(4) C(4)-C(5)-C(6) 120.5(3) C(31)-C(32)-C(27) 119.3(3) C(1)-C(6)-C(5) 120.4(3) C(31)-C(32)-C(43) 118.1(3) C(1)-C(6)-C(17) 120.3(2) C(27)-C(32)-C(43) 122.6(3) C(5)-C(6)-C(17) 119.3(2) C(34)-C(33)-C(38) 116.6(3) C(12)-C(7)-C(8) 117.1(3) C(34)-C(33)-C(28) 122.6(3) C(12)-C(7)-C(2) 123.1(2) C(38)-C(33)-C(28) 120.8(3) C(8)-C(7)-C(2) 119.8(3) C(33)-C(34)-C(35) 121.3(3) C(7)-C(8)-C(9) 121.7(3) C(36)-C(35)-C(34) 121.9(3) C(10)-C(9)-C(8) 121.5(3) C(35)-C(36)-C(37) 115.9(4) C(9)-C(10)-C(11) 116.6(3) C(35)-C(36)-C(39) 123.7(3) C(9)-C(10)-C(13) 120.2(3) C(37)-C(36)-C(39) 120.4(3) C(11)-C(10)-C(13) 123.2(3) C(38)-C(37)-C(36) 122.0(3) C(12)-C(11)-C(10) 121.9(3) C(37)-C(38)-C(33) 121.8(3) C(11)-C(12)-C(7) 121.2(3) C(36)-C(39)-C(42) 112.8(3) C(15)-C(13)-C(14) 112.0(5) C(36)-C(39)-C(40) 109.5(4) C(15)-C(13)-C(10) 113.1(3) C(42)-C(39)-C(40) 108.3(5) C(14)-C(13)-C(10) 109.8(4) C(36)-C(39)-C(41) 110.5(4) C(15)-C(13)-C(16) 106.9(5) C(42)-C(39)-C(41) 108.1(4) C(14)-C(13)-C(16) 105.1(6) C(40)-C(39)-C(41) 107.3(4) C(10)-C(13)-C(16) 109.7(3) C(44)-C(43)-C(48) 116.4(3) C(22)-C(17)-C(18) 117.4(3) C(44)-C(43)-C(32) 121.5(3) C(22)-C(17)-C(6) 120.9(3) C(48)-C(43)-C(32) 122.0(2) C(18)-C(17)-C(6) 121.8(3) C(43)-C(44)-C(45) 121.8(3) C(19)-C(18)-C(17) 121.1(3) C(46)-C(45)-C(44) 121.9(3) C(18)-C(19)-C(20) 121.7(3) C(45)-C(46)-C(47) 115.8(3) C(21)-C(20)-C(19) 117.0(3) C(45)-C(46)-C(49) 124.1(3) C(21)-C(20)-C(23) 122.5(3) C(47)-C(46)-C(49) 120.1(3)
179
Table 6 (con’t). Bond angles [°] for R2GaCl (2) Atoms Angle Atoms Angle C(19)-C(20)-C(23) 120.5(3) C(48)-C(47)-C(46) 122.4(3) C(20)-C(21)-C(22) 121.2(3) C(47)-C(48)-C(43) 121.6(3) C(17)-C(22)-C(21) 121.6(3) C(46)-C(49)-C(50) 110.0(3) C(20)-C(23)-C(26) 108.6(4) C(46)-C(49)-C(51) 109.1(3) C(20)-C(23)-C(24) 110.5(3) C(50)-C(49)-C(51) 109.5(3) C(26)-C(23)-C(24) 108.3(5) C(46)-C(49)-C(52) 111.8(3) C(20)-C(23)-C(25) 110.8(4) C(50)-C(49)-C(52) 108.0(3) C(51)-C(49)-C(52) 108.3(3)
180
Structural Data for RAlBr2(Et2O) (3) (R = 2,6-(4-t-BuC6H4)2C6H3-)
Table 7. Crystal data and structural refinement for (2,6-(4-t-BuC6H4)2C6H3)AlBr2(Et2O) (3) Empirical formula C60H78Al2Br4O2 Formula weight 1204.82 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/n Unit cell dimensions a = 24.1758(17) Å b = 11.5810(8) Å c = 24.6206(16) Å = 90°
= 118.4790(10)°
= 90°
Volume 6059.1(7) Å3 Z, Calculated density 4, 1.321 Mg/m3 Absorption coefficient 2.724 mm-1 F(000) 2480 Crystal size 0.40 x 0.30 x 0.25 mm Theta range for data collection 1.92 to 25.00 deg. Limiting indices -26<=h<=28, -13<=k<=13, -28<=l<=29 Reflections collected / unique 35885 / 10646 [R(int) = 0.0323] Completeness to theta 25.00 99.7 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 10646 / 0 / 596 Goodness-of-fit on F^2 1.013 Final R indices [I>2sigma(I)] R1 = 0.0554, wR2 = 0.1523 R indices (all data) R1 = 0.0981, wR2 = 0.1852 Largest diff. peak and hole 0.616 and -0.752 e.Å-3
181
Table 8. Bond Lengths [Å] for RAlBr2(Et2O) (3) Atoms Distance Atoms Distance Al(1)-O(1) 1.877(4) C(23)-C(25') 1.44(2) Al(1)-C(1) 1.979(5) C(23)-C(26') 1.52(2) Al(1)-Br(2) 2.3013(16) C(23)-C(24) 1.592(19) Al(1)-Br(1) 2.3173(17) C(23)-C(25) 1.624(16) Al(2)-O(2) 1.875(4) C(23)-C(24') 1.55(2) Al(2)-C(31) 1.975(5) C(23)-C(26) 1.655(16) Al(2)-Br(4) 2.2999(17) C(24)-C(24') 0.58(3) Al(2)-Br(3) 2.3151(17) C(24)-C(26) 2.17(2) O(1)-C(29) 1.365(16) C(25)-C(25') 1.31(3) O(1)-C(27) 1.496(13) C(25')-C(26') 1.32(3) O(1)-C(29') 1.94(5) C(26)-C(26') 1.28(2) O(1)-C(27') 1.62(2) C(27)-C(28') 1.11(3) O(2)-C(57') 1.34(2) C(27)-C(27') 1.27(2) O(2)-C(59') 1.377(15) C(27)-C(28) 1.58(2) O(2)-C(57) 1.653(15) C(27')-C(28) 1.14(2) O(2)-C(59) 1.67(2) C(27')-C(28') 1.53(3) C(1)-C(6) 1.411(6) C(28)-C(28') 0.93(3) C(1)-C(2) 1.409(6) C(29)-C(30') 1.00(6) C(2)-C(3) 1.386(7) C(29)-C(30) 1.30(3) C(2)-C(7) 1.487(7) C(29')-C(30') 1.08(7) C(3)-C(4) 1.371(7) C(29')-C(30) 1.68(6) C(4)-C(5) 1.364(7) C(30)-C(30') 0.80(6) C(5)-C(6) 1.405(7) C(31)-C(36) 1.417(7) C(6)-C(17) 1.497(7) C(31)-C(32) 1.412(7) C(7)-C(8) 1.382(7) C(32)-C(33) 1.390(7) C(7)-C(12) 1.399(7) C(32)-C(37) 1.496(7) C(8)-C(9) 1.374(7) C(33)-C(34) 1.378(7) C(9)-C(10) 1.382(8) C(34)-C(35) 1.370(7) C(10)-C(11) 1.374(7) C(35)-C(36) 1.386(7) C(10)-C(13) 1.531(8) C(36)-C(47) 1.499(7) C(11)-C(12) 1.383(7) C(37)-C(38) 1.378(7) C(13)-C(15') 1.40(2) C(37)-C(42) 1.380(7) C(13)-C(16) 1.474(18) C(38)-C(39) 1.383(7) C(13)-C(14) 1.528(18) C(39)-C(40) 1.390(8) C(13)-C(16') 1.67(2) C(40)-C(41) 1.377(8) C(13)-C(14') 1.637(17) C(40)-C(43) 1.540(8) C(13)-C(15) 1.723(17) C(41)-C(42) 1.384(7) C(14)-C(14') 0.65(2) C(43)-C(46') 1.518(18) C(15)-C(15') 0.75(2) C(43)-C(44) 1.617(16) C(15')-C(16) 1.86(3) C(43)-C(44') 1.52(2)
182
Table 8 (con’t). Bond Lengths [Å] for RAlBr2(Et2O) (3) Atoms Distance Atoms Distance C(16)-C(16') 0.89(2) C(43)-C(45) 1.59(2) C(17)-C(18) 1.378(7) C(43)-C(46) 1.63(2) C(17)-C(22) 1.395(7) C(43)-C(45') 1.600(18) C(18)-C(19) 1.375(7) C(44)-C(44') 0.76(2) C(19)-C(20) 1.391(7) C(44')-C(45) 2.06(3) C(20)-C(21) 1.383(8) C(45)-C(45') 0.84(2) C(20)-C(23) 1.533(8) C(45')-C(46') 2.09(3) C(21)-C(22) 1.374(8) C(46)-C(46') 0.73(3) C(47)-C(52) 1.395(7) C(57)-C(58') 1.27(3) C(47)-C(48) 1.393(7) C(57)-C(58) 1.54(2) C(48)-C(49) 1.377(7) C(57')-C(58) 1.31(2) C(49)-C(50) 1.398(7) C(57')-C(58') 1.43(3) C(50)-C(51) 1.391(7) C(58)-C(58') 1.69(3) C(50)-C(53) 1.521(7) C(59)-C(59') 0.60(3) C(51)-C(52) 1.378(7) C(59)-C(60) 1.52(3) C(53)-C(56) 1.513(8) C(59)-C(60') 1.82(3) C(53)-C(55) 1.554(9) C(59')-C(60') 1.53(3) C(53)-C(54) 1.551(8) C(59')-C(60) 1.60(3) C(57)-C(57') 0.71(2) C(60)-C(60') 1.10(3)
183
Table 9. Bond angles [°] for RAlBr2(Et2O) (3)
Atoms Angles Atoms Angle
O(1)-Al(1)-C(1) 106.64(19) C(1)-C(2)-C(7) 120.4(4)
O(1)-Al(1)-Br(2) 104.27(14) C(2)-C(3)-C(4) 120.4(5)
C(1)-Al(1)-Br(2) 120.08(15) C(3)-C(4)-C(5) 120.1(5)
O(1)-Al(1)-Br(1) 97.97(14) C(4)-C(5)-C(6) 120.8(5)
C(1)-Al(1)-Br(1) 117.46(15) C(1)-C(6)-C(5) 120.2(5)
Br(2)-Al(1)-Br(1) 107.22(6) C(1)-C(6)-C(17) 122.8(4)
O(2)-Al(2)-C(31) 103.93(19) C(5)-C(6)-C(17) 116.9(4)
O(2)-Al(2)-Br(4) 106.57(15) C(8)-C(7)-C(12) 117.2(5)
C(31)-Al(2)-Br(4) 121.72(15) C(8)-C(7)-C(2) 121.0(4)
O(2)-Al(2)-Br(3) 97.43(14) C(12)-C(7)-C(2) 121.8(4)
C(31)-Al(2)-Br(3) 117.59(16) C(7)-C(8)-C(9) 121.0(5)
Br(4)-Al(2)-Br(3) 106.17(6) C(10)-C(9)-C(8) 122.2(5)
C(29)-O(1)-C(27) 110.8(8) C(9)-C(10)-C(11) 116.7(5)
C(29)-O(1)-C(29') 17.3(19) C(9)-C(10)-C(13) 120.7(5) C(27)-O(1)-C(29') 108.9(16) C(11)-C(10)-C(13) 122.5(5)
C(29)-O(1)-C(27') 114.5(11) C(10)-C(11)-C(12) 122.1(5) C(27)-O(1)-C(27') 47.8(9) C(11)-C(12)-C(7) 120.4(5)
C(29')-O(1)-C(27') 126.8(18) C(15')-C(13)-C(16) 80.5(12) C(29)-O(1)-Al(1) 118.8(7) C(15')-C(13)-C(14) 121.2(12)
C(27)-O(1)-Al(1) 129.4(5) C(16)-C(13)-C(14) 109.4(11)
C(29')-O(1)-Al(1) 115.2(15) C(15')-C(13)-C(10) 117.2(10) C(27')-O(1)-Al(1) 113.5(9) C(16)-C(13)-C(10) 110.5(8)
C(57')-O(2)-C(59') 98.3(12) C(14)-C(13)-C(10) 112.6(8)
C(57')-O(2)-C(57) 24.6(11) C(15')-C(13)-C(16') 110.0(13) C(59')-O(2)-C(57) 114.2(9) C(16)-C(13)-C(16') 32.0(9)
C(57')-O(2)-C(59) 116.8(13) C(14)-C(13)-C(16') 83.1(11) C(59')-O(2)-C(59) 19.9(10) C(10)-C(13)-C(16') 106.1(9)
C(57)-O(2)-C(59) 134.1(10) C(15')-C(13)-C(14') 107.6(11)
C(57')-O(2)-Al(2) 125.5(10) C(16)-C(13)-C(14') 129.0(10) C(59')-O(2)-Al(2) 135.9(7) C(14)-C(13)-C(14') 23.5(7)
C(57)-O(2)-Al(2) 108.8(5) C(10)-C(13)-C(14') 109.3(7)
C(59)-O(2)-Al(2) 116.5(9) C(16')-C(13)-C(14') 106.2(11) C(6)-C(1)-C(2) 116.9(4) C(15')-C(13)-C(15) 25.2(9)
C(6)-C(1)-Al(1) 122.9(3) C(16)-C(13)-C(15) 105.5(10) C(2)-C(1)-Al(1) 119.3(3) C(14)-C(13)-C(15) 114.3(10)
C(3)-C(2)-C(1) 121.3(4) C(10)-C(13)-C(15) 104.3(7)
C(3)-C(2)-C(7) 118.3(4) C(16')-C(13)-C(15) 135.0(10)
184
Table 9 (con’t). Bond angles [°] for RAlBr2(Et2O) (3)
Atoms Angles Atoms Angle
C(14')-C(13)-C(15) 94.0(8) C(26')-C(23)-C(26) 47.2(8) C(14')-C(14)-C(13) 88(3) C(20)-C(23)-C(26) 104.8(7)
C(14)-C(14')-C(13) 69(2) C(24)-C(23)-C(26) 83.9(9)
C(15')-C(15)-C(13) 52(2) C(25)-C(23)-C(26) 143.3(8) C(15)-C(15')-C(13) 102(3) C(24')-C(23)-C(26) 102.9(11)
C(15)-C(15')-C(16) 153(3) C(24')-C(24)-C(23) 76(3)
C(13)-C(15')-C(16) 51.5(9) C(24')-C(24)-C(26) 120(4) C(16')-C(16)-C(13) 86(2) C(23)-C(24)-C(26) 49.3(7)
C(16')-C(16)-C(15') 130(2) C(24)-C(24')-C(23) 83(4) C(13)-C(16)-C(15') 47.9(8) C(25')-C(25)-C(23) 57.7(12)
C(16)-C(16')-C(13) 61.6(18) C(26')-C(25')-C(25) 138(2)
C(18)-C(17)-C(22) 117.2(5) C(26')-C(25')-C(23) 66.4(15) C(18)-C(17)-C(6) 121.2(4) C(25)-C(25')-C(23) 72.0(15)
C(22)-C(17)-C(6) 121.5(5) C(26')-C(26)-C(23) 60.7(11)
C(17)-C(18)-C(19) 120.9(5) C(26')-C(26)-C(24) 101.1(14) C(20)-C(19)-C(18) 122.4(5) C(23)-C(26)-C(24) 46.8(7)
C(21)-C(20)-C(19) 116.4(5) C(26)-C(26')-C(25') 130(2)
C(21)-C(20)-C(23) 122.2(5) C(26)-C(26')-C(23) 72.0(12)
C(19)-C(20)-C(23) 121.4(6) C(25')-C(26')-C(23) 60.7(14) C(22)-C(21)-C(20) 121.5(5) C(28')-C(27)-C(27') 80(2)
C(21)-C(22)-C(17) 121.6(5) C(28')-C(27)-O(1) 145(2) C(25')-C(23)-C(26') 52.9(11) C(27')-C(27)-O(1) 71.4(13)
C(25')-C(23)-C(20) 114.9(10) C(28')-C(27)-C(28) 35.2(16) C(26')-C(23)-C(20) 110.5(8) C(27')-C(27)-C(28) 45.7(12)
C(25')-C(23)-C(24) 132.2(12) O(1)-C(27)-C(28) 111.0(11) C(26')-C(23)-C(24) 122.2(11) C(28)-C(27')-C(27) 82(2)
C(20)-C(23)-C(24) 110.3(8) C(28)-C(27')-C(28') 37.4(15)
C(25')-C(23)-C(25) 50.3(11) C(27)-C(27')-C(28') 45.6(14) C(26')-C(23)-C(25) 102.8(10) C(28)-C(27')-O(1) 132(2)
C(20)-C(23)-C(25) 106.2(7) C(27)-C(27')-O(1) 60.8(12)
C(24)-C(23)-C(25) 103.0(9) C(28')-C(27')-O(1) 104.1(19) C(25')-C(23)-C(24') 119.3(13) C(28')-C(28)-C(27') 94(3)
C(26')-C(23)-C(24') 132.5(12) C(28')-C(28)-C(27) 43(2) C(20)-C(23)-C(24') 113.1(10) C(27')-C(28)-C(27) 52.4(15)
C(24)-C(23)-C(24') 21.0(10) C(27)-C(28')-C(28) 101(3)
C(25)-C(23)-C(24') 82.3(10) C(27)-C(28')-C(27') 54.7(16) C(25')-C(23)-C(26) 98.5(12) C(28)-C(28')-C(27') 94(3)
185
Table 9 (Continued). Bond angles [°] for RAlBr2•(Et2O) (3)
Atoms Angles Atoms Angle
C(30')-C(29)-C(30) 38(4) C(46')-C(43)-C(44') 126.9(12) C(30')-C(29)-O(1) 80(2) C(40)-C(43)-C(44') 112.1(9)
C(30)-C(29)-O(1) 123.3(17) C(44)-C(43)-C(44') 27.9(8)
C(30')-C(29')-C(30) 23(4) C(46')-C(43)-C(45) 112.8(12) C(30')-C(29')-O(1) 94(6) C(40)-C(43)-C(45) 106.5(8)
C(30)-C(29')-O(1) 80(2) C(44)-C(43)-C(45) 109.2(10)
C(30')-C(30)-C(29) 50(5) C(44')-C(43)-C(45) 82.9(12) C(30')-C(30)-C(29') 32(5) C(46')-C(43)-C(46) 26.6(9)
C(29)-C(30)-C(29') 26(2) C(40)-C(43)-C(46) 104.9(9) C(30)-C(30')-C(29) 92(6) C(44)-C(43)-C(46) 85.1(10)
C(30)-C(30')-C(29') 126(8) C(44')-C(43)-C(46) 111.1(12)
C(29)-C(30')-C(29') 42(3) C(45)-C(43)-C(46) 137.0(12) C(36)-C(31)-C(32) 116.7(4) C(46')-C(43)-C(45') 83.9(11)
C(36)-C(31)-Al(2) 122.5(4) C(40)-C(43)-C(45') 110.4(7)
C(32)-C(31)-Al(2) 119.4(3) C(44)-C(43)-C(45') 129.4(9) C(33)-C(32)-C(31) 121.0(4) C(44')-C(43)-C(45') 108.3(11)
C(33)-C(32)-C(37) 118.5(4) C(45)-C(43)-C(45') 30.4(8) C(31)-C(32)-C(37) 120.4(4) C(46)-C(43)-C(45') 110.0(11)
C(32)-C(33)-C(34) 120.5(5) C(44')-C(44)-C(43) 69(2)
C(35)-C(34)-C(33) 119.7(5) C(44)-C(44')-C(43) 83(2) C(34)-C(35)-C(36) 121.0(5) C(44)-C(44')-C(45) 130(3)
C(31)-C(36)-C(35) 120.7(5) C(43)-C(44')-C(45) 50.0(9)
C(31)-C(36)-C(47) 121.9(4) C(45')-C(45)-C(43) 75(2)
C(35)-C(36)-C(47) 117.4(4) C(45')-C(45)-C(44') 115(2) C(38)-C(37)-C(42) 117.5(5) C(43)-C(45)-C(44') 47.1(8)
C(38)-C(37)-C(32) 120.6(4) C(45)-C(45')-C(43) 74(2) C(42)-C(37)-C(32) 121.9(5) C(45)-C(45')-C(46') 118(2)
C(37)-C(38)-C(39) 120.9(5) C(43)-C(45')-C(46') 46.4(7) C(38)-C(39)-C(40) 122.0(5) C(46')-C(46)-C(43) 68(2)
C(41)-C(40)-C(39) 116.3(5) C(46)-C(46')-C(43) 85(3)
C(41)-C(40)-C(43) 122.7(5) C(46)-C(46')-C(45') 134(3) C(39)-C(40)-C(43) 121.0(5) C(43)-C(46')-C(45') 49.7(8)
C(40)-C(41)-C(42) 121.9(5) C(52)-C(47)-C(48) 116.6(5) C(37)-C(42)-C(41) 121.2(5) C(52)-C(47)-C(36) 122.5(5)
C(46')-C(43)-C(40) 110.8(8) C(48)-C(47)-C(36) 120.8(4)
C(46')-C(43)-C(44) 106.0(10) C(47)-C(48)-C(49) 121.1(5) C(40)-C(43)-C(44) 111.5(7) C(48)-C(49)-C(50) 122.6(5)
186
Table 9 (con’t). Bond angles [°] for RAlBr2•(Et2O) (3)
Atoms Angles Atoms Angle
C(51)-C(50)-C(49) 115.8(5) C(57')-C(58)-C(57) 27.2(11) C(51)-C(50)-C(53) 124.1(5) C(57')-C(58)-C(58') 55.0(13)
C(49)-C(50)-C(53) 120.1(5) C(57)-C(58)-C(58') 45.8(10)
C(52)-C(51)-C(50) 121.8(5) C(57)-C(58')-C(57') 63(2)
C(51)-C(52)-C(47) 122.0(5) C(57)-C(58')-C(58) 60.8(14) C(50)-C(53)-C(56) 109.9(5) C(57')-C(58')-C(58) 48.6(13)
C(50)-C(53)-C(55) 110.0(5) C(59')-C(59)-C(60) 86(3)
C(56)-C(53)-C(55) 109.6(6) C(59')-C(59)-C(60') 52(3) C(50)-C(53)-C(54) 111.5(5) C(60)-C(59)-C(60') 37.2(14)
C(56)-C(53)-C(54) 107.8(5) C(59')-C(59)-O(2) 51(3)
C(55)-C(53)-C(54) 107.9(5) C(60)-C(59)-O(2) 101.4(19) C(57')-C(57)-C(58') 88(3) C(60')-C(59)-O(2) 88.3(13)
C(57')-C(57)-C(58) 58(3) C(59)-C(59')-O(2) 109(3) C(58')-C(57)-C(58) 73.4(14) C(59)-C(59')-C(60') 110(3)
C(57')-C(57)-O(2) 52(3) O(2)-C(59')-C(60') 114.0(14)
C(58')-C(57)-O(2) 103.1(15) C(59)-C(59')-C(60) 72(3)
C(58)-C(57)-O(2) 109.4(11) O(2)-C(59')-C(60) 112.5(15)
C(57)-C(57')-C(58) 95(3) C(60')-C(59')-C(60) 41.3(13)
C(57)-C(57')-O(2) 104(3) C(60')-C(60)-C(59) 86(3)
C(58)-C(57')-O(2) 161(2) C(60')-C(60)-C(59') 66(2)
C(57)-C(57')-C(58') 63(2) C(59)-C(60)-C(59') 22.2(11)
C(58)-C(57')-C(58') 76.4(18) C(60)-C(60')-C(59') 73(2)
O(2)-C(57')-C(58') 113(2) C(60)-C(60')-C(59) 56(2)
C(59')-C(60')-C(59) 29.7(12)
187
Structural Data for ([RAlCl(OEt2)]2O (4) (R =2,6-(4-t-BuC6H4)2C6H3-)
Table 10. Crystal data and structural refinement for [2,6-(4-t-BuC6H4)2C6H3AlCl(OEt2)]2O (4) Empirical formula C63.50H82Al2Cl2O3 Formula weight 1018.15 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, C2/c Unit cell dimensions a = 66.721(4) Å b = 10.1736(6) Å c = 19.2750(10) Å = 90°
= 105.9820(10)°
= 90°
Volume 12578.1(12) A3 Z, Calculated density 8, 1.075 Mg/m3 Absorption coefficient 0.171 mm-1 F(000) 4376 Crystal size 0.80 x 0.40 x 0.20 mm Theta range for data collection 1.90 to 25.00 deg. Limiting indices -74<=h<=79, -12<=k<=12, -20<=l<=22 Reflections collected / unique 36893 / 10985 [R(int) = 0.0328] Completeness to theta 25.00 99.3 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9665 and 0.8751 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 10985 / 0 / 630 Goodness-of-fit on F^2 1.054 Final R indices [I>2sigma(I)] R1 = 0.1121, wR2 = 0.3410 R indices (all data) R1 = 0.1489, wR2 = 0.4049 Extinction coefficient 0.0026(6) Largest diff. peak and hole 1.917 and -0.570 e.Å-3
188
Table 11. Bond Lengths [Å] for [RAlCl(OEt2)]2O (4)
Atoms Distance Atoms Distance
Al(1)-O(1) 1.696(4) C(10)-C(11) 1.396(8)
Al(1)-O(2) 1.906(4) C(10)-C(13) 1.547(9)
Al(1)-C(1) 2.001(5) C(11)-C(12) 1.374(8)
Al(1)-Cl(1) 2.354(2) C(13)-C(14) 1.504(12)
Al(2)-O(1) 1.691(4) C(13)-C(16) 1.509(16)
Al(2)-O(3) 1.906(4) C(13)-C(15) 1.568(13)
Al(2)-C(31) 2.013(5) C(17)-C(22) 1.373(9)
Al(2)-Cl(2) 2.3939(19) C(17)-C(18) 1.379(9)
O(2)-C(29) 1.429(9) C(18)-C(19) 1.406(12)
O(2)-C(28) 1.476(10) C(19)-C(20) 1.360(13)
O(3)-C(59) 1.447(7) C(20)-C(21) 1.358(11)
O(3)-C(58) 1.477(7) C(20)-C(23) 1.512(12)
C(1)-C(2) 1.409(7) C(21)-C(22) 1.378(8)
C(1)-C(6) 1.418(8) C(23)-C(25) 1.38(3)
C(2)-C(3) 1.384(8) C(23)-C(25') 1.47(3)
C(2)-C(7) 1.477(8) C(23)-C(26) 1.54(3)
C(3)-C(4) 1.405(10) C(23)-C(24') 1.37(4)
C(4)-C(5) 1.377(10) C(23)-C(24) 1.61(3)
C(5)-C(6) 1.418(8) C(23)-C(26') 1.71(3)
C(6)-C(17) 1.484(8) C(24)-C(24') 1.18(4)
C(7)-C(8) 1.384(8) C(24)-C(25') 2.09(4)
C(7)-C(12) 1.396(8) C(24')-C(26) 1.24(4)
C(8)-C(9) 1.390(8) C(25)-C(25') 1.22(4)
C(9)-C(10) 1.404(9) C(25)-C(26') 1.35(4)
189
Table 11 (con’t). Bond Lengths [Å] for [RAlCl(OEt2)]2O (4)
Atoms Distance Atoms Distance
C(26)-C(26') 1.46(4) C(48)-C(49) 1.389(8)
C(27)-C(28) 1.219(18) C(49)-C(50) 1.396(8)
C(29)-C(30) 1.356(13) C(50)-C(51) 1.391(8)
C(31)-C(32) 1.404(7) C(50)-C(53) 1.512(9)
C(31)-C(36) 1.438(7) C(51)-C(52) 1.400(8)
C(32)-C(33) 1.390(8) C(53)-C(54') 1.39(4)
C(32)-C(37) 1.492(8) C(53)-C(56) 1.54(2)
C(33)-C(34) 1.378(9) C(53)-C(55') 1.48(2)
C(34)-C(35) 1.370(8) C(53)-C(54) 1.57(2)
C(35)-C(36) 1.401(7) C(53)-C(56') 1.35(5)
C(36)-C(47) 1.477(7) C(53)-C(55) 1.52(3)
C(37)-C(38) 1.382(8) C(54)-C(54') 0.86(4)
C(37)-C(42) 1.392(8) C(54')-C(56) 1.80(5)
C(38)-C(39) 1.379(8) C(55)-C(55') 0.71(3)
C(39)-C(40) 1.400(10) C(55)-C(56') 1.45(5)
C(40)-C(41) 1.383(10) C(56)-C(56') 0.89(5)
C(40)-C(43) 1.549(10) C(57)-C(58) 1.516(11)
C(41)-C(42) 1.345(9) C(59)-C(60) 1.437(12)
C(43)-C(46) 1.409(15) C(61)-C(63)#1 1.34(2)
C(43)-C(45) 1.431(15) C(61)-C(62) 1.26(2)
C(43)-C(44) 1.612(17) C(62)-C(63) 1.35(2)
C(47)-C(52) 1.383(7) C(63)-C(61)#1 1.34(2)
C(47)-C(48) 1.391(7) C(63)-C(64) 1.50(4
190
Table 12. Bond angles [°] for [RAlCl(OEt2)]2O (4) Atoms Angle Atoms Angle O(1)-Al(1)-Cl(1) 108.85(15) C(14)-C(13)-C(16) 108.6(11) O(2)-Al(1)-Cl(1) 95.92(15) C(10)-C(13)-C(16) 107.4(7) C(1)-Al(1)-Cl(1) 117.90(17) C(14)-C(13)-C(15) 106.9(8) O(1)-Al(2)-O(3) 104.80(18) C(10)-C(13)-C(15) 106.3(7) O(1)-Al(2)-C(31) 120.68(19) C(16)-C(13)-C(15) 115.4(11) O(3)-Al(2)-C(31) 105.40(19) C(22)-C(17)-C(18) 115.2(6) O(1)-Al(2)-Cl(2) 110.77(14) C(22)-C(17)-C(6) 121.5(5) O(3)-Al(2)-Cl(2) 97.23(14) C(18)-C(17)-C(6) 123.1(6) C(31)-Al(2)-Cl(2) 114.45(15) C(17)-C(18)-C(19) 122.6(8) Al(2)-O(1)-Al(1) 160.0(2) C(20)-C(19)-C(18) 120.6(7) C(29)-O(2)-C(28) 111.7(7) C(19)-C(20)-C(21) 116.6(7) C(29)-O(2)-Al(1) 127.6(5) C(19)-C(20)-C(23) 119.2(9) C(28)-O(2)-Al(1) 118.2(5) C(21)-C(20)-C(23) 124.2(10) C(59)-O(3)-C(58) 114.7(5) C(22)-C(21)-C(20) 123.0(8) C(59)-O(3)-Al(2) 122.0(4) C(21)-C(22)-C(17) 121.8(6) C(58)-O(3)-Al(2) 118.1(3) C(25)-C(23)-C(25') 50.6(15) C(2)-C(1)-C(6) 117.5(5) C(25)-C(23)-C(26) 101(2) C(2)-C(1)-Al(1) 120.1(4) C(25')-C(23)-C(26) 144.1(19) C(6)-C(1)-Al(1) 122.1(4) C(25)-C(23)-C(24') 129(2) C(3)-C(2)-C(1) 120.9(5) C(25')-C(23)-C(24') 126(2) C(3)-C(2)-C(7) 116.2(5) C(26)-C(23)-C(24') 50.2(18) C(1)-C(2)-C(7) 122.8(5) C(25)-C(23)-C(20) 118.2(16) C(2)-C(3)-C(4) 121.6(6) C(25')-C(23)-C(20) 108.7(15) C(3)-C(4)-C(5) 118.2(6) C(26)-C(23)-C(20) 104.3(14) C(4)-C(5)-C(6) 121.2(6) C(24')-C(23)-C(20) 110.6(18) C(1)-C(6)-C(5) 120.2(6) C(25)-C(23)-C(24) 120.1(18) C(1)-C(6)-C(17) 125.6(5) C(25')-C(23)-C(24) 85.2(17) C(5)-C(6)-C(17) 114.2(5) C(26)-C(23)-C(24) 95.2(16) C(8)-C(7)-C(12) 116.8(5) C(24')-C(23)-C(24) 45.9(18) C(8)-C(7)-C(2) 121.2(5) C(20)-C(23)-C(24) 112.6(14) C(12)-C(7)-C(2) 121.9(5) C(25)-C(23)-C(26') 50.6(17) C(7)-C(8)-C(9) 121.9(5) C(25')-C(23)-C(26') 101.0(18) C(8)-C(9)-C(10) 120.6(6) C(26)-C(23)-C(26') 53.1(16) C(11)-C(10)-C(9) 117.4(6) C(24')-C(23)-C(26') 98(2) C(11)-C(10)-C(13) 121.7(6) C(20)-C(23)-C(26') 110.6(14) C(9)-C(10)-C(13) 120.9(6) C(24)-C(23)-C(26') 131.6(16) C(10)-C(11)-C(12) 120.9(6) C(24')-C(24)-C(23) 56(2) C(7)-C(12)-C(11) 122.3(5) C(24')-C(24)-C(25') 98(3) C(14)-C(13)-C(10) 112.3(6) C(23)-C(24)-C(25') 44.8(12)
191
Table 12 (con’t). Bond angles [°] for [RAlCl(OEt2)]2O (4) Atoms Angle Atoms Angle C(24)-C(24')-C(26) 147(4) C(37)-C(42)-C(41) 123.2(6) C(24)-C(24')-C(23) 78(3) C(46)-C(43)-C(45) 111.9(13) C(26)-C(24')-C(23) 72(3) C(46)-C(43)-C(40) 113.8(8) C(25')-C(25)-C(23) 69(2) C(45)-C(43)-C(40) 109.6(8) C(25')-C(25)-C(26') 145(4) C(46)-C(43)-C(44) 107.2(10) C(23)-C(25)-C(26') 77(2) C(45)-C(43)-C(44) 107.9(11) C(25)-C(25')-C(23) 61(2) C(40)-C(43)-C(44) 106.2(8) C(25)-C(25')-C(24) 100(3) C(52)-C(47)-C(48) 117.3(5) C(23)-C(25')-C(24) 50.1(13) C(52)-C(47)-C(36) 121.2(5) C(24')-C(26)-C(26') 120(3) C(48)-C(47)-C(36) 121.4(4) C(24')-C(26)-C(23) 58(2) C(49)-C(48)-C(47) 121.6(5) C(26')-C(26)-C(23) 69(2) C(48)-C(49)-C(50) 121.6(5) C(26)-C(26')-C(25) 106(3) C(51)-C(50)-C(49) 116.4(5) C(26)-C(26')-C(23) 57.6(18) C(51)-C(50)-C(53) 122.0(5) C(25)-C(26')-C(23) 52.1(18) C(49)-C(50)-C(53) 121.6(6) C(27)-C(28)-O(2) 125.1(16) C(50)-C(51)-C(52) 122.1(5) C(30)-C(29)-O(2) 121.8(8) C(51)-C(52)-C(47) 120.9(5) C(32)-C(31)-C(36) 116.9(4) C(54')-C(53)-C(50) 117.4(19) C(32)-C(31)-Al(2) 123.9(4) C(54')-C(53)-C(56) 76(2) C(36)-C(31)-Al(2) 119.1(4) C(50)-C(53)-C(56) 107.8(9) C(31)-C(32)-C(33) 120.9(5) C(54')-C(53)-C(55') 118(2) C(31)-C(32)-C(37) 123.3(5) C(50)-C(53)-C(55') 113.7(9) C(33)-C(32)-C(37) 115.6(5) C(56)-C(53)-C(55') 118.2(12) C(34)-C(33)-C(32) 121.3(6) C(54')-C(53)-C(54) 33.1(18) C(35)-C(34)-C(33) 119.6(5) C(50)-C(53)-C(54) 109.0(9) C(34)-C(35)-C(36) 120.9(5) C(56)-C(53)-C(54) 108.8(11) C(35)-C(36)-C(31) 120.2(5) C(55')-C(53)-C(54) 98.7(12) C(35)-C(36)-C(47) 116.1(5) C(54')-C(53)-C(56') 101(3) C(31)-C(36)-C(47) 123.5(4) C(50)-C(53)-C(56') 117(2) C(38)-C(37)-C(42) 115.8(5) C(56)-C(53)-C(56') 35(2) C(38)-C(37)-C(32) 122.3(5) C(55')-C(53)-C(56') 85(2) C(42)-C(37)-C(32) 121.7(5) C(54)-C(53)-C(56') 128(2) C(37)-C(38)-C(39) 121.6(6) C(54')-C(53)-C(55) 131(2) C(38)-C(39)-C(40) 121.6(7) C(50)-C(53)-C(55) 111.6(12) C(41)-C(40)-C(39) 116.1(6) C(56)-C(53)-C(55) 95.3(14) C(41)-C(40)-C(43) 122.9(7) C(55')-C(53)-C(55) 27.3(12) C(39)-C(40)-C(43) 120.9(8) C(54)-C(53)-C(55) 122.7(15) C(40)-C(41)-C(42) 121.8(6) C(56')-C(53)-C(55) 60(2)
192
Table 12 (con’t). Bond angles [°] for [RAlCl(OEt2)]2O (4) Atoms Angle Atoms Angle C(54')-C(54)-C(53) 62(3) C(53)-C(56)-C(54') 48.2(15) C(54)-C(54')-C(53) 85(4) C(56)-C(56')-C(53) 84(4) C(54)-C(54')-C(56) 141(5) C(56)-C(56')-C(55) 149(5) C(53)-C(54')-C(56) 55.8(17) C(53)-C(56')-C(55) 65(2) C(55')-C(55)-C(56') 121(4) O(3)-C(58)-C(57) 112.2(6) C(55')-C(55)-C(53) 74(3) O(3)-C(59)-C(60) 115.5(8) C(56')-C(55)-C(53) 54(2) C(63)#1-C(61)-C(62) 118.1(17) C(55)-C(55')-C(53) 79(3) C(61)-C(62)-C(63) 117.1(17) C(56')-C(56)-C(53) 61(4) C(61)#1-C(63)-C(64) 119(2) C(56')-C(56)-C(54') 98(4) C(61)#1-C(63)-C(62) 124.5(19) C(64)-C(63)-C(62) 116(2)
193
Structural Data for R3In (5) (R = 2,6-(4-t-BuC6H4)2C6H3-)
Table 13. Crystal data and structural refinement for R3In (5) Empirical formula C82H97InO Formula weight 1213.42 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 11.6636(13)Å b = 15.0818(16) Å c = 21.278(2) Å = 103.912(2)°
= 96.812(2)°
= 90.555(2)°
Volume 3604.6(7) Å3 Z, Calculated density 2, 1.118 Mg/m3 Absorption coefficient 0.370 mm-1 F(000) 1292 Crystal size 0.45 x 0.35 x 0.25 mm Theta range for data collection 1.76 to 25.00 deg. Limiting indices -13<=h<=13, -17<=k<=17, -25<=l<=22 Reflections collected / unique 21456 / 12638 [R(int) = 0.0204] Completeness to theta = 25.00 99.6 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 12638 / 0 / 745 Goodness-of-fit on F^2 1.076 Final R indices [I>2sigma(I)] R1 = 0.0533, wR2 = 0.1457 R indices (all data) R1 = 0.0628, wR2 = 0.1559 Largest diff. peak and hole 0.777 and -0.528 e. Å-3
194
Table 14. Bond Lengths [Å] for R3In (5) Atoms Distance Atoms Distance In(1)-C(53) 2.192(3) C(27)-C(28) 1.401(5) In(1)-C(1) 2.199(3) C(27)-C(32) 1.419(5) In(1)-C(27) 2.200(3) C(28)-C(29) 1.406(6) C(1)-C(2) 1.409(5) C(28)-C(33) 1.494(5) C(1)-C(6) 1.408(5) C(29)-C(30) 1.374(7) C(2)-C(3) 1.410(6) C(30)-C(31) 1.363(7) C(2)-C(7) 1.483(6) C(31)-C(32) 1.410(6) C(3)-C(4) 1.376(7) C(32)-C(43) 1.476(6) C(4)-C(5) 1.374(6) C(33)-C(38) 1.394(6) C(5)-C(6) 1.389(5) C(33)-C(34) 1.391(6) C(6)-C(17) 1.487(5) C(34)-C(35) 1.389(6) C(7)-C(8) 1.374(6) C(35)-C(36) 1.385(6) C(7)-C(12) 1.397(5) C(36)-C(37) 1.392(5) C(8)-C(9) 1.394(6) C(36)-C(39) 1.533(6) C(9)-C(10) 1.380(6) C(37)-C(38) 1.377(5) C(10)-C(11) 1.387(6) C(39)-C(41') 1.46(2) C(10)-C(13) 1.535(6) C(39)-C(40') 1.55(3) C(11)-C(12) 1.376(6) C(39)-C(42) 1.506(13) C(13)-C(16) 1.532(8) C(39)-C(40) 1.592(12) C(13)-C(15) 1.527(8) C(39)-C(41) 1.589(14) C(13)-C(14) 1.537(8) C(39)-C(42') 1.679(19) C(17)-C(18) 1.379(6) C(40)-C(40') 1.63(3) C(17)-C(22) 1.394(5) C(40)-C(41') 2.02(2) C(18)-C(19) 1.381(6) C(40')-C(42) 1.22(3) C(19)-C(20) 1.387(7) C(40')-C(42') 2.22(3) C(20)-C(21) 1.391(6) C(41)-C(41') 0.70(2) C(20)-C(23) 1.531(7) C(42)-C(42') 1.104(19) C(21)-C(22) 1.370(5) C(43)-C(44) 1.388(5) C(23)-C(26) 1.482(16) C(43)-C(48) 1.392(6) C(23)-C(24) 1.540(18) C(44)-C(45) 1.373(6) C(23)-C(25') 1.65(2) C(45)-C(46) 1.391(6) C(23)-C(25) 1.600(19) C(46)-C(47) 1.389(6) C(23)-C(26') 1.622(18) C(46)-C(49) 1.540(7) C(23)-C(24') 1.697(17) C(47)-C(48) 1.376(6) C(24)-C(24') 0.67(2) C(49)-C(52') 1.48(2) C(24)-C(25) 2.03(3) C(49)-C(50') 1.50(3) C(25)-C(25') 0.81(3) C(49)-C(50) 1.554(13) C(25')-C(26) 2.09(3) C(49)-C(51) 1.559(14) C(26)-C(26') 0.879(19) C(49)-C(51') 1.61(2)
195
Table 14 (con’t) Bond Lengths [Å] for R3In (5) Atoms Distance Atoms Distance C(49)-C(52) 1.626(14) C(65)-C(66) 1.533(8) C(50)-C(50') 1.42(3) C(65)-C(67) 1.557(8) C(50)-C(51') 1.83(2) C(69)-C(74) 1.381(5) C(50')-C(52) 1.45(3) C(69)-C(70) 1.390(6) C(51)-C(52') 1.12(2) C(70)-C(71) 1.390(6) C(51)-C(51') 1.39(2) C(71)-C(72) 1.375(6) C(52)-C(52') 1.62(2) C(72)-C(73) 1.387(6) C(53)-C(54) 1.409(5) C(72)-C(75) 1.541(6) C(53)-C(58) 1.403(5) C(73)-C(74) 1.375(5) C(54)-C(55) 1.403(5) C(75)-C(78') 1.49(3) C(54)-C(59) 1.487(5) C(75)-C(76') 1.49(2) C(55)-C(56) 1.353(7) C(75)-C(77) 1.522(14) C(56)-C(57) 1.374(6) C(75)-C(76) 1.562(13) C(57)-C(58) 1.398(5) C(75)-C(78) 1.639(13) C(58)-C(69) 1.487(5) C(75)-C(77') 1.70(3) C(59)-C(60) 1.384(6) C(76)-C(76') 0.74(2) C(59)-C(64) 1.388(6) C(76')-C(77') 1.79(3) C(60)-C(61) 1.374(6) C(77)-C(78') 1.06(3) C(61)-C(62) 1.386(6) C(77)-C(77') 1.55(3) C(62)-C(63) 1.383(6) C(78)-C(78') 1.54(3) C(62)-C(65) 1.540(6) O(1)-C(81) 1.411(16) C(63)-C(64) 1.376(6) O(1)-C(80) 1.465(18) C(65)-C(68) 1.487(9) C(79)-C(80) 1.61(2) C(81)-C(82) 1.399(17)
196
Table 15. Bond angles [°] for R3In (5) Atoms Angle Atoms Angle C(53)-In(1)-C(1) 120.29(13) C(22)-C(21)-C(20) 121.6(4) C(53)-In(1)-C(27) 124.86(13) C(21)-C(22)-C(17) 122.0(4) C(1)-In(1)-C(27) 114.79(13) C(26)-C(23)-C(20) 113.7(8) C(2)-C(1)-C(6) 117.8(3) C(26)-C(23)-C(24) 126.5(10) C(2)-C(1)-In(1) 117.3(3) C(20)-C(23)-C(24) 113.1(7) C(6)-C(1)-In(1) 124.0(3) C(26)-C(23)-C(25') 83.4(11) C(1)-C(2)-C(3) 119.9(4) C(20)-C(23)-C(25') 105.4(9) C(1)-C(2)-C(7) 122.4(3) C(24)-C(23)-C(25') 107.7(12) C(3)-C(2)-C(7) 117.6(3) C(26)-C(23)-C(25) 108.0(10) C(4)-C(3)-C(2) 120.6(4) C(20)-C(23)-C(25) 107.7(8) C(5)-C(4)-C(3) 120.0(4) C(24)-C(23)-C(25) 80.7(11) C(4)-C(5)-C(6) 120.6(4) C(25')-C(23)-C(25) 29.0(9) C(5)-C(6)-C(1) 120.9(4) C(26)-C(23)-C(26') 32.5(7) C(5)-C(6)-C(17) 116.3(4) C(20)-C(23)-C(26') 105.3(7) C(1)-C(6)-C(17) 122.8(3) C(24)-C(23)-C(26') 109.7(10) C(8)-C(7)-C(12) 117.0(4) C(25')-C(23)-C(26') 115.7(11) C(8)-C(7)-C(2) 122.2(3) C(25)-C(23)-C(26') 137.5(10) C(12)-C(7)-C(2) 120.8(4) C(26)-C(23)-C(24') 112.8(9) C(7)-C(8)-C(9) 121.1(4) C(20)-C(23)-C(24') 110.8(7) C(10)-C(9)-C(8) 122.4(4) C(24)-C(23)-C(24') 23.2(7) C(9)-C(10)-C(11) 116.0(4) C(25')-C(23)-C(24') 128.2(11) C(9)-C(10)-C(13) 124.1(4) C(25)-C(23)-C(24') 103.1(10) C(11)-C(10)-C(13) 119.9(4) C(26')-C(23)-C(24') 89.0(9) C(12)-C(11)-C(10) 122.3(4) C(24')-C(24)-C(23) 92(3) C(11)-C(12)-C(7) 121.3(4) C(24')-C(24)-C(25) 140(3) C(16)-C(13)-C(10) 108.8(4) C(23)-C(24)-C(25) 50.9(8) C(16)-C(13)-C(15) 107.8(5) C(24)-C(24')-C(23) 65(2) C(10)-C(13)-C(15) 111.9(4) C(25')-C(25)-C(23) 79(3) C(16)-C(13)-C(14) 110.0(5) C(25')-C(25)-C(24) 124(3) C(10)-C(13)-C(14) 109.6(4) C(23)-C(25)-C(24) 48.4(7) C(15)-C(13)-C(14) 108.7(5) C(25)-C(25')-C(23) 72(2) C(18)-C(17)-C(22) 116.6(4) C(25)-C(25')-C(26) 111(3) C(18)-C(17)-C(6) 122.0(4) C(23)-C(25')-C(26) 44.9(8) C(22)-C(17)-C(6) 121.3(3) C(26')-C(26)-C(23) 82.6(17) C(17)-C(18)-C(19) 121.4(4) C(26')-C(26)-C(25') 134(2) C(20)-C(19)-C(18) 122.2(4) C(23)-C(26)-C(25') 51.7(8) C(19)-C(20)-C(21) 116.2(4) C(26)-C(26')-C(23) 64.9(16) C(19)-C(20)-C(23) 122.2(5) C(28)-C(27)-C(32) 117.6(3) C(21)-C(20)-C(23) 121.5(5) C(28)-C(27)-In(1) 121.4(3)
197
Table 15 (con’t). Bond angles [°] for R3In (5) Atoms Angle Atoms Angle C(32)-C(27)-In(1) 119.7(3) C(40)-C(39)-C(42') 142.9(8) C(27)-C(28)-C(29) 120.9(4) C(41)-C(39)-C(42') 79.4(8) C(27)-C(28)-C(33) 123.6(3) C(39)-C(40)-C(40') 57.4(10) C(29)-C(28)-C(33) 115.5(4) C(39)-C(40)-C(41') 45.8(6) C(30)-C(29)-C(28) 120.3(4) C(40')-C(40)-C(41') 94.1(13) C(31)-C(30)-C(29) 120.2(4) C(42)-C(40')-C(39) 64.8(15) C(30)-C(31)-C(32) 121.1(4) C(42)-C(40')-C(40) 121(2) C(31)-C(32)-C(27) 119.8(4) C(39)-C(40')-C(40) 60.2(11) C(31)-C(32)-C(43) 116.7(3) C(42)-C(40')-C(42') 15.8(10) C(27)-C(32)-C(43) 123.4(3) C(39)-C(40')-C(42') 48.9(9) C(38)-C(33)-C(34) 117.2(4) C(40)-C(40')-C(42') 106.3(15) C(38)-C(33)-C(28) 121.5(3) C(41')-C(41)-C(39) 66(2) C(34)-C(33)-C(28) 121.1(4) C(41)-C(41')-C(39) 87(2) C(33)-C(34)-C(35) 120.6(4) C(41)-C(41')-C(40) 139(3) C(36)-C(35)-C(34) 122.5(4) C(39)-C(41')-C(40) 51.5(7) C(35)-C(36)-C(37) 116.3(4) C(42')-C(42)-C(40') 147(2) C(35)-C(36)-C(39) 123.2(4) C(42')-C(42)-C(39) 78.4(12) C(37)-C(36)-C(39) 120.5(4) C(40')-C(42)-C(39) 68.2(15) C(38)-C(37)-C(36) 122.0(4) C(42)-C(42')-C(39) 61.5(11) C(37)-C(38)-C(33) 121.4(4) C(42)-C(42')-C(40') 17.5(12) C(41')-C(39)-C(40') 126.2(13) C(39)-C(42')-C(40') 44.0(8) C(41')-C(39)-C(42) 122.0(10) C(44)-C(43)-C(48) 116.2(4) C(40')-C(39)-C(42) 47.0(10) C(44)-C(43)-C(32) 121.7(4) C(41')-C(39)-C(36) 116.5(8) C(48)-C(43)-C(32) 121.9(4) C(40')-C(39)-C(36) 112.3(11) C(43)-C(44)-C(45) 121.6(4) C(42)-C(39)-C(36) 114.8(6) C(46)-C(45)-C(44) 122.6(4) C(41')-C(39)-C(40) 82.7(9) C(45)-C(46)-C(47) 115.5(4) C(40')-C(39)-C(40) 62.4(11) C(45)-C(46)-C(49) 122.5(4) C(42)-C(39)-C(40) 106.7(7) C(47)-C(46)-C(49) 122.0(4) C(36)-C(39)-C(40) 106.7(5) C(48)-C(47)-C(46) 122.2(4) C(41')-C(39)-C(41) 26.3(8) C(47)-C(48)-C(43) 121.8(4) C(40')-C(39)-C(41) 138.6(12) C(52')-C(49)-C(50') 114.5(14) C(42)-C(39)-C(41) 110.6(8) C(52')-C(49)-C(46) 113.5(9) C(36)-C(39)-C(41) 108.9(6) C(50')-C(49)-C(46) 106.0(11) C(40)-C(39)-C(41) 108.9(7) C(52')-C(49)-C(50) 132.1(10) C(41')-C(39)-C(42') 101.5(11) C(50')-C(49)-C(50) 55.2(11) C(40')-C(39)-C(42') 87.1(12) C(46)-C(49)-C(50) 114.2(6) C(42)-C(39)-C(42') 40.1(7) C(52')-C(49)-C(51) 43.1(8) C(36)-C(39)-C(42') 104.2(7) C(50')-C(49)-C(51) 143.8(12)
198
Table 15 (con’t). Bond angles [°] for R3In (5) Atoms Angle Atoms Angle C(46)-C(49)-C(51) 109.5(6) C(57)-C(58)-C(53) 120.6(3) C(50)-C(49)-C(51) 113.5(7) C(57)-C(58)-C(69) 116.7(3) C(52')-C(49)-C(51') 93.9(11) C(53)-C(58)-C(69) 122.6(3) C(50')-C(49)-C(51') 125.0(13) C(60)-C(59)-C(64) 116.2(4) C(46)-C(49)-C(51') 103.5(8) C(60)-C(59)-C(54) 123.4(4) C(50)-C(49)-C(51') 70.5(8) C(64)-C(59)-C(54) 120.2(4) C(51)-C(49)-C(51') 52.0(8) C(59)-C(60)-C(61) 121.7(4) C(52')-C(49)-C(52) 62.8(9) C(62)-C(61)-C(60) 122.1(4) C(50')-C(49)-C(52) 55.0(11) C(61)-C(62)-C(63) 116.1(4) C(46)-C(49)-C(52) 111.0(6) C(61)-C(62)-C(65) 120.5(4) C(50)-C(49)-C(52) 103.6(7) C(63)-C(62)-C(65) 123.3(4) C(51)-C(49)-C(52) 104.4(7) C(64)-C(63)-C(62) 121.8(4) C(51')-C(49)-C(52) 143.8(9) C(63)-C(64)-C(59) 121.9(4) C(50')-C(50)-C(49) 60.4(12) C(68)-C(65)-C(62) 110.1(5) C(50')-C(50)-C(51') 116.0(14) C(68)-C(65)-C(66) 111.8(7) C(49)-C(50)-C(51') 56.3(7) C(62)-C(65)-C(66) 108.8(4) C(52)-C(50')-C(49) 67.0(13) C(68)-C(65)-C(67) 108.2(6) C(52)-C(50')-C(50) 122(2) C(62)-C(65)-C(67) 111.9(5) C(49)-C(50')-C(50) 64.4(13) C(66)-C(65)-C(67) 106.0(6) C(52')-C(51)-C(51') 128.1(18) C(74)-C(69)-C(70) 116.2(4) C(52')-C(51)-C(49) 64.5(13) C(74)-C(69)-C(58) 122.7(3) C(51')-C(51)-C(49) 66.1(10) C(70)-C(69)-C(58) 121.0(4) C(51)-C(51')-C(49) 61.9(10) C(69)-C(70)-C(71) 121.8(4) C(51)-C(51')-C(50) 107.0(13) C(72)-C(71)-C(70) 121.5(4) C(49)-C(51')-C(50) 53.2(7) C(71)-C(72)-C(73) 116.5(4) C(50')-C(52)-C(49) 58.0(12) C(71)-C(72)-C(75) 122.6(4) C(50')-C(52)-C(52') 109.1(15) C(73)-C(72)-C(75) 120.9(4) C(49)-C(52)-C(52') 54.1(8) C(74)-C(73)-C(72) 122.1(4) C(51)-C(52')-C(49) 72.4(14) C(73)-C(74)-C(69) 121.9(4) C(51)-C(52')-C(52) 132.8(19) C(78')-C(75)-C(76') 129.4(15) C(49)-C(52')-C(52) 63.1(9) C(78')-C(75)-C(77) 41.3(12) C(54)-C(53)-C(58) 117.9(3) C(76')-C(75)-C(77) 113.9(10) C(54)-C(53)-In(1) 120.3(3) C(78')-C(75)-C(72) 116.8(13) C(58)-C(53)-In(1) 121.8(2) C(76')-C(75)-C(72) 113.5(9) C(53)-C(54)-C(55) 119.6(4) C(77)-C(75)-C(72) 110.6(6) C(53)-C(54)-C(59) 123.0(3) C(78')-C(75)-C(76) 126.1(13) C(55)-C(54)-C(59) 117.3(3) C(76')-C(75)-C(76) 27.9(8) C(56)-C(55)-C(54) 121.3(4) C(77)-C(75)-C(76) 133.3(7) C(55)-C(56)-C(57) 120.3(4) C(72)-C(75)-C(76) 111.6(6) C(56)-C(57)-C(58) 120.1(4) C(78')-C(75)-C(78) 58.6(13)
199
Table 15 (con’t). Bond angles [°] for R3In (5) Atoms Angle Atoms Angle C(76')-C(75)-C(78) 111.9(9) C(75)-C(76')-C(77') 61.8(11) C(77)-C(75)-C(78) 99.8(7) C(78')-C(77)-C(75) 67.5(19) C(72)-C(75)-C(78) 105.9(6) C(78')-C(77)-C(77') 131(2) C(76)-C(75)-C(78) 86.9(7) C(75)-C(77)-C(77') 67.2(11) C(78')-C(75)-C(77') 97.0(15) C(76')-C(77')-C(75) 50.4(10) C(76')-C(75)-C(77') 67.8(11) C(76')-C(77')-C(77) 98.0(15) C(77)-C(75)-C(77') 57.2(9) C(75)-C(77')-C(77) 55.6(10) C(72)-C(75)-C(77') 101.2(9) C(78')-C(78)-C(75) 55.7(12) C(76)-C(75)-C(77') 95.5(10) C(78)-C(78')-C(77) 137(3) C(78)-C(75)-C(77') 149.6(10) C(78)-C(78')-C(75) 65.7(14) C(76')-C(76)-C(75) 70(2) C(77)-C(78')-C(75) 71.2(19) C(76)-C(76')-C(75) 82(2) C(81)-O(1)-C(80) 116.0(13) C(76)-C(76')-C(77') 143(3) O(1)-C(80)-C(79) 106.6(16) O(1)-C(81)-C(82) 111.1(12)
200
Structural Data for [(R GaCl3][Li(OEt2)2] (6) (R = 2,6-(4-Me-C6H4)2C6H3-)
Table 16. Crystal data and structural refinement for [R GaCl3][Li(OEt2)2] (6) Empirical formula C28H37Cl3Ga Li O2 Formula weight 588.59 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Orthorhombic, Pbca Unit cell dimensions a = 10.3332(17) Å b = 17.310(3) Å c = 35.168(6) Å = 90°
= 90°
= 90° Volume 6290.6(18) Å3 Z, Calculated density 8, 1.243 Mg/m3 Absorption coefficient 1.150 mm-1 F(000) 2448 Crystal size 0.60 x 0.48 x 0.38 mm Theta range for data collection 2.29 to 25.00 deg. Limiting indices -12<=h<=12, -20<=k<=19, -41<=l<=41 Reflections collected / unique 35380 / 5522 [R(int) = 0.0265] Completeness to theta 25.00 99.6 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.6690 and 0.5452 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 5522 / 0 / 292 Goodness-of-fit on F^2 1.06 Final R indices [I>2sigma(I)] R1 = 0.0616, wR2 = 0.1803
201
Table 17. Bond Lengths [Å] for [R GaCl3][Li(OEt2)2] (6)
Atoms Distance Atoms Distance
Ga(1)-C(1) 1.970(4) C(16)-C(17) 1.354(9)
Ga(1)-Cl(1) 2.2503(14) C(17)-C(18) 1.387(11)
Ga(1)-Cl(2) 2.2530(13) C(17)-C(20) 1.514(10)
Ga(1)-Cl(3) 2.2759(13) C(18)-C(19) 1.397(10)
Ga(1)-Li(1) 3.213(9) Li(1)-O(1) 1.928(10)
Cl(1)-Li(1) 2.406(10) Li(1)-O(2) 1.926(10)
Cl(2)-Li(1) 2.397(10) O(1)-C(23) 1.407(9)
C(1)-C(2) 1.406(6) O(1)-C(22) 1.478(18)
C(1)-C(6) 1.422(6) O(1)-C(22') 1.52(2)
C(2)-C(3) 1.390(6) O(2)-C(25') 1.46(3)
C(2)-C(7) 1.487(7) O(2)-C(27) 1.477(10)
C(3)-C(4) 1.348(9) O(2)-C(25) 1.80(5)
C(4)-C(5) 1.368(9) C(21)-C(22') 1.01(3)
C(5)-C(6) 1.397(7) C(21)-C(21') 1.35(3)
C(6)-C(14) 1.478(8) C(21)-C(22) 1.72(3)
C(7)-C(8) 1.362(7) C(21')-C(22) 0.99(3)
C(7)-C(12) 1.404(7) C(21')-C(22') 1.06(3)
C(8)-C(9) 1.384(9) C(22)-C(22') 0.81(2)
C(9)-C(10) 1.357(10) C(23)-C(24) 1.380(12)
C(10)-C(11) 1.388(9) C(25)-C(25') 0.77(5)
C(10)-C(13) 1.527(9) C(25)-C(26') 0.89(5)
C(11)-C(12) 1.375(7) C(25)-C(26) 1.43(5)
C(14)-C(15) 1.395(8) C(25')-C(26) 0.97(4)
C(14)-C(19) 1.394(7) C(25')-C(26') 1.27(4)
C(15)-C(16) 1.403(8) C(27)-C(28) 1.358(12)
202
Table 18. Bond angles [°] for[R GaCl3][Li(OEt2)2] (6)
Atoms Angle Atoms Angle
C(1)-Ga(1)-Cl(1) 113.22(13) C(19)-C(14)-C(6) 121.5(5)
C(1)-Ga(1)-Cl(2) 109.80(13) C(14)-C(15)-C(16) 121.7(5)
Cl(1)-Ga(1)-Cl(2) 95.25(5) C(17)-C(16)-C(15) 121.1(7)
C(1)-Ga(1)-Cl(3) 122.49(13) C(16)-C(17)-C(18) 118.2(7)
Cl(1)-Ga(1)-Cl(3) 105.56(6) C(16)-C(17)-C(20) 122.1(9)
Cl(2)-Ga(1)-Cl(3) 106.97(6) C(18)-C(17)-C(20) 119.7(8)
C(1)-Ga(1)-Li(1) 113.8(2) C(17)-C(18)-C(19) 121.4(6)
Cl(1)-Ga(1)-Li(1) 48.40(19) C(14)-C(19)-C(18) 120.9(6)
Cl(2)-Ga(1)-Li(1) 48.17(19) O(1)-Li(1)-O(2) 113.8(5)
Cl(3)-Ga(1)-Li(1) 123.69(17) O(1)-Li(1)-Cl(1) 108.9(5)
Ga(1)-Cl(1)-Li(1) 87.2(2) O(2)-Li(1)-Cl(1) 116.9(5)
Ga(1)-Cl(2)-Li(1) 87.4(2) O(1)-Li(1)-Cl(2) 109.4(4)
C(2)-C(1)-C(6) 118.0(4) O(2)-Li(1)-Cl(2) 117.3(5)
C(2)-C(1)-Ga(1) 120.6(3) Cl(1)-Li(1)-Cl(2) 87.7(3)
C(6)-C(1)-Ga(1) 120.4(3) O(1)-Li(1)-Ga(1) 109.1(4)
C(3)-C(2)-C(1) 120.0(5) O(2)-Li(1)-Ga(1) 137.2(5)
C(3)-C(2)-C(7) 117.4(4) Cl(1)-Li(1)-Ga(1) 44.38(15)
C(1)-C(2)-C(7) 122.6(4) Cl(2)-Li(1)-Ga(1) 44.46(15)
C(4)-C(3)-C(2) 121.7(5) C(23)-O(1)-C(22) 119.7(8)
C(3)-C(4)-C(5) 119.5(5) C(23)-O(1)-C(22') 115.1(10)
C(4)-C(5)-C(6) 122.0(5) C(22)-O(1)-C(22') 31.3(10)
C(5)-C(6)-C(1) 118.6(5) C(23)-O(1)-Li(1) 121.8(6)
C(5)-C(6)-C(14) 119.0(5) C(22)-O(1)-Li(1) 117.5(7)
C(1)-C(6)-C(14) 122.4(4) C(22')-O(1)-Li(1) 119.0(9)
C(8)-C(7)-C(12) 116.7(5) C(25')-O(2)-C(27) 108.9(11)
C(8)-C(7)-C(2) 123.1(5) C(25')-O(2)-C(25) 24.5(17)
C(12)-C(7)-C(2) 120.2(4) C(27)-O(2)-C(25) 113.3(16)
C(7)-C(8)-C(9) 121.7(6) C(25')-O(2)-Li(1) 121.2(11)
C(10)-C(9)-C(8) 121.9(6) C(27)-O(2)-Li(1) 124.3(6)
C(9)-C(10)-C(11) 117.5(6) C(25)-O(2)-Li(1) 122.4(15)
C(9)-C(10)-C(13) 120.6(8) C(22')-C(21)-C(21') 51.3(19)
C(11)-C(10)-C(13) 121.9(8) C(22')-C(21)-C(22) 16.5(16)
C(12)-C(11)-C(10) 120.9(6) C(21')-C(21)-C(22) 35.0(15)
C(11)-C(12)-C(7) 121.2(5) C(22)-C(21')-C(22') 46(2)
C(15)-C(14)-C(19) 116.6(5) C(22)-C(21')-C(21) 94(3)
C(15)-C(14)-C(6) 121.8(4) C(22')-C(21')-C(21) 48(2)
203
Table 18 (con’t). Bond angles [°] for[R GaCl3][Li(OEt2)2] (6)
Atoms Angle Atoms Angle
C(21')-C(22)-C(22') 72(2) C(25')-C(25)-C(26) 40(3)
C(21')-C(22)-O(1) 146(3) C(26')-C(25)-C(26) 83(4)
C(22')-C(22)-O(1) 77(2) C(25')-C(25)-O(2) 52(4)
C(21')-C(22)-C(21) 51(2) C(26')-C(25)-O(2) 103(5)
C(22')-C(22)-C(21) 21(2) C(26)-C(25)-O(2) 91(3)
O(1)-C(22)-C(21) 96.4(13) C(25)-C(25')-C(26) 110(5)
C(22)-C(22')-C(21) 143(4) C(25)-C(25')-O(2) 104(5)
C(22)-C(22')-C(21') 62(2) C(26)-C(25')-O(2) 144(4)
C(21)-C(22')-C(21') 81(3) C(25)-C(25')-C(26') 44(4)
C(22)-C(22')-O(1) 72(2) C(26)-C(25')-C(26') 89(3)
C(21)-C(22')-O(1) 142(3) O(2)-C(25')-C(26') 106(2)
C(21')-C(22')-O(1) 132(3) C(25')-C(26)-C(25) 30(3)
O(1)-C(23)-C(24) 115.8(9) C(25)-C(26')-C(25') 37(4)
C(25')-C(25)-C(26') 100(7) O(2)-C(27)-C(28) 111.1(8)
204
Structural Data for [R InCl3][Li(OEt2)(THF)] (7) (R = 2,6-(4-Me-C6H4)2C6H3-)
Table 19. Crystal data and structural refinement for [R InCl3][Li(OEt2)(THF)] (7)
Empirical formula C56H68Cl6In2Li2O4 Formula weight 1261.32 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 9.4678(10) Å b = 18.8936(19) Å c = 18.952(2) Å = 91.346(2)°
= 91.652(2)°
= 94.416(2)°
Volume 3377.5(6) Å3 Z, Calculated density 2, 1.240 Mg/m3 Absorption coefficient 0.956 mm-1 F(000) 1284 Crystal size 0.12 x 0.10 x 0.04 mm Theta range for data collection 2.15 to 28.32 deg. Limiting indices -12<=h<=12, -25<=k<=25, -25<=l<=25 Reflections collected / unique 47241 / 16756 [R(int) = 0.2334] Completeness to theta = 28.32 99.50% Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9628 and 0.8939 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 16756 / 447 / 792 Goodness-of-fit on F^2 1.005 Final R indices [I>2sigma(I)] R1 = 0.0949, wR2 = 0.2234 R indices (all data) R1 = 0.3550, wR2 = 0.3030 Largest diff. peak and hole 1.275 and -0.546 e.Å-3
205
Table 2.20. Bond Lengths [Å] for [R InCl3][Li(OEt2)(THF)] (7)
Atoms Distance Atoms Distance In(1)-C(1) 2.133(13) O(1)-C(22) 1.51(4) In(1)-Cl(3) 2.398(4) C(21)-C(22) 1.53(3) In(1)-Cl(2) 2.438(4) C(23)-C(24) 1.66(4) In(1)-Cl(1) 2.442(4) C(21')-C(22') 1.555(19) In(1)-Li(1) 3.35(2) C(23')-C(24') 1.66(4) Cl(1)-Li(1) 2.34(3) O(2)-C(25') 1.31(3) Cl(2)-Li(1) 2.50(3) O(2)-C(28') 1.37(2) Li(1)-O(1) 1.85(3) O(2)-C(25) 1.486(19) Li(1)-O(2) 1.91(3) O(2)-C(28) 1.490(19) C(1)-C(2) 1.415(18) C(25)-C(26) 1.55(4) C(1)-C(6) 1.387(17) C(26)-C(27) 1.54(4) C(2)-C(3) 1.393(19) C(27)-C(28) 1.36(4) C(2)-C(14) 1.52(2) C(25')-C(26') 1.55(3) C(3)-C(4) 1.30(2) C(26')-C(27') 1.53(4) C(4)-C(5) 1.37(2) C(27')-C(28') 1.36(4) C(5)-C(6) 1.446(18) In(2)-C(29) 2.125(13) C(6)-C(7) 1.500(18) In(2)-Cl(6) 2.402(4) C(7)-C(8) 1.347(17) In(2)-Cl(5) 2.419(4) C(7)-C(12) 1.390(19) In(2)-Cl(4) 2.433(4) C(8)-C(9) 1.34(2) In(2)-Li(2) 3.23(2) C(9)-C(10) 1.37(3) Cl(4)-Li(2) 2.27(3) C(10)-C(11) 1.39(2) Cl(5)-Li(2) 2.43(3) C(10)-C(13) 1.60(3) Li(2)-O(3') 1.924(18) C(11)-C(12) 1.44(2) Li(2)-O(4') 1.957(17) C(14)-C(15) 1.41(2) Li(2)-O(4) 2.001(19) C(14)-C(19) 1.434(19) Li(2)-O(3) 1.91(4) C(15)-C(16) 1.38(2) C(29)-C(30) 1.407(17) C(16)-C(17) 1.34(2) C(29)-C(34) 1.410(17) C(17)-C(18) 1.32(2) C(30)-C(31) 1.380(17) C(17)-C(20) 1.36(2) C(30)-C(42) 1.442(17) C(18)-C(19) 1.41(2) C(31)-C(32) 1.392(19) O(1)-C(23) 1.60(4) C(32)-C(33) 1.38(2) O(1)-C(23') 0.87(3) C(33)-C(34) 1.360(18) O(1)-C(22') 1.528(19) C(34)-C(35) 1.428(18)
206
Table 20 (con’t). Bond Lengths [Å] for [R InCl3][Li(OEt2)(THF)] (7)
Atoms Distance Atoms Distance C(35)-C(40) 1.361(18) C(50)-C(51) 1.29(3) C(35)-C(36) 1.414(19) C(51)-C(52) 1.60(3) C(36)-C(37) 1.44(2) O(3')-C(52') 1.26(4) C(37)-C(38) 1.43(2) O(3')-C(49') 1.45(8) C(38)-C(39) 1.38(3) C(49')-C(50') 1.96(3) C(38)-C(41) 1.59(2) C(50')-C(51') 1.29(3) C(39)-C(40) 1.35(2) C(51')-C(52') 1.60(3) C(42)-C(47) 1.361(17) O(4)-C(53) 1.43(3) C(42)-C(43) 1.382(18) O(4)-C(56) 1.45(3) C(43)-C(44) 1.403(19) C(53)-C(54) 1.33(3) C(44)-C(45) 1.39(2) C(54)-C(55) 1.57(4) C(45)-C(46) 1.39(2) C(55)-C(56) 1.41(3) C(45)-C(48) 1.516(19) O(4')-C(53') 1.41(2) C(46)-C(47) 1.374(18) O(4')-C(56') 1.44(2) O(3)-C(52) 1.25(5) C(53')-C(54') 1.33(3) O(3)-C(49) 1.44(8) C(54')-C(55') 1.57(3) C(49)-C(50) 1.95(3) C(55')-C(56') 1.40(3)
207
Table 2.21. Bond angles [°] for [R InCl3][Li(OEt2)(THF)] (7)
Atoms Distance Atoms Distance C(1)-In(1)-Cl(3) 121.2(4) C(9)-C(10)-C(11) 122(2) C(1)-In(1)-Cl(2) 115.3(4) C(9)-C(10)-C(13) 131(2) Cl(3)-In(1)-Cl(2) 104.74(16) C(11)-C(10)-C(13) 108(2) C(1)-In(1)-Cl(1) 115.7(4) C(10)-C(11)-C(12) 114.9(18) Cl(3)-In(1)-Cl(1) 104.00(14) C(7)-C(12)-C(11) 122.3(16) Cl(2)-In(1)-Cl(1) 91.33(14) C(15)-C(14)-C(19) 115.5(19) C(1)-In(1)-Li(1) 134.7(6) C(15)-C(14)-C(2) 122.7(16) Cl(3)-In(1)-Li(1) 104.1(4) C(19)-C(14)-C(2) 121.7(17) Cl(2)-In(1)-Li(1) 48.0(5) C(16)-C(15)-C(14) 121.1(17) Cl(1)-In(1)-Li(1) 44.1(5) C(15)-C(16)-C(17) 123.7(19) Li(1)-Cl(1)-In(1) 89.1(6) C(18)-C(17)-C(16) 117(2) In(1)-Cl(2)-Li(1) 85.6(6) C(18)-C(17)-C(20) 117(2) O(1)-Li(1)-O(2) 110.9(14) C(16)-C(17)-C(20) 126(2) O(1)-Li(1)-Cl(1) 112.7(15) C(17)-C(18)-C(19) 125(2) O(2)-Li(1)-Cl(1) 114.9(12) C(14)-C(19)-C(18) 117.6(18) O(1)-Li(1)-Cl(2) 121.4(12) C(23)-O(1)-C(23') 19(4) O(2)-Li(1)-Cl(2) 103.5(13) C(23)-O(1)-C(22') 123(2) Cl(1)-Li(1)-Cl(2) 92.4(8) C(23')-O(1)-C(22') 139(4) O(1)-Li(1)-In(1) 137.7(13) C(23)-O(1)-C(22) 94(3) O(2)-Li(1)-In(1) 111.4(10) C(23')-O(1)-C(22) 101(5) Cl(1)-Li(1)-In(1) 46.7(4) C(22')-O(1)-C(22) 47(3) Cl(2)-Li(1)-In(1) 46.4(4) C(23)-O(1)-Li(1) 133(2) C(2)-C(1)-C(6) 117.0(14) C(23')-O(1)-Li(1) 118(3) C(2)-C(1)-In(1) 121.0(12) C(22')-O(1)-Li(1) 103.2(18) C(6)-C(1)-In(1) 121.7(10) C(22)-O(1)-Li(1) 128(3) C(1)-C(2)-C(3) 121.8(16) O(1)-C(22)-C(21) 93(3) C(1)-C(2)-C(14) 119.0(14) O(1)-C(23)-C(24) 94(4) C(3)-C(2)-C(14) 119.2(16) O(1)-C(22')-C(21') 98.1(16) C(4)-C(3)-C(2) 121.4(18) O(1)-C(23')-C(24') 148(4) C(3)-C(4)-C(5) 119.9(19) C(25')-O(2)-C(28') 113(2) C(4)-C(5)-C(6) 121.5(16) C(25')-O(2)-C(25) 64(3) C(1)-C(6)-C(5) 118.1(14) C(28')-O(2)-C(25) 70(3) C(1)-C(6)-C(7) 119.4(13) C(25')-O(2)-C(28) 88(3) C(5)-C(6)-C(7) 122.4(15) C(28')-O(2)-C(28) 53(3) C(8)-C(7)-C(12) 117.6(15) C(25)-O(2)-C(28) 98(3) C(8)-C(7)-C(6) 123.5(14) C(25')-O(2)-Li(1) 116.1(18) C(12)-C(7)-C(6) 118.6(16) C(28')-O(2)-Li(1) 128.3(18) C(7)-C(8)-C(9) 122.5(17) C(25)-O(2)-Li(1) 148(3) C(10)-C(9)-C(8) 120.9(19) C(28)-O(2)-Li(1) 115(3)
208
Table 2.21 (con’t). Bond angles [°] for [R InCl3][Li(OEt2)(THF)] (7)
Atoms Distance Atoms Distance O(2)-C(25)-C(26) 78(3) C(31)-C(30)-C(29) 118.3(14) C(25)-C(26)-C(27) 94(4) C(31)-C(30)-C(42) 119.7(15) C(28)-C(27)-C(26) 104(3) C(29)-C(30)-C(42) 122.0(13) C(27)-C(28)-O(2) 97(2) C(34)-C(33)-C(32) 116.7(16) O(2)-C(25')-C(26') 107(3) C(33)-C(34)-C(35) 115.9(15) C(25')-C(26')-C(27') 94(3) C(33)-C(34)-C(29) 122.5(15) C(28')-C(27')-C(26') 106(3) C(35)-C(34)-C(29) 121.6(14) C(27')-C(28')-O(2) 103(3) C(40)-C(35)-C(36) 118.4(16) C(29)-In(2)-Cl(6) 119.8(3) C(40)-C(35)-C(34) 120.3(15) C(29)-In(2)-Cl(5) 116.3(4) C(36)-C(35)-C(34) 121.2(16) Cl(6)-In(2)-Cl(5) 104.62(15) C(35)-C(36)-C(37) 117.7(16) C(29)-In(2)-Cl(4) 116.2(4) C(36)-C(37)-C(38) 121.8(18) Cl(6)-In(2)-Cl(4) 104.69(15) C(37)-C(38)-C(39) 115(2) Cl(5)-In(2)-Cl(4) 90.85(14) C(37)-C(38)-C(41) 116(2) C(29)-In(2)-Li(2) 139.7(5) C(39)-C(38)-C(41) 128(2) Cl(6)-In(2)-Li(2) 100.5(4) C(40)-C(39)-C(38) 123.1(19) Cl(5)-In(2)-Li(2) 48.3(5) C(39)-C(40)-C(35) 123.6(17) Cl(4)-In(2)-Li(2) 44.5(5) C(47)-C(42)-C(43) 116.8(14) Li(2)-Cl(4)-In(2) 86.8(6) C(47)-C(42)-C(30) 121.4(14) In(2)-Cl(5)-Li(2) 83.7(6) C(43)-C(42)-C(30) 121.7(14) O(3')-Li(2)-O(4') 106.1(16) C(42)-C(43)-C(44) 121.9(14) O(4)-Li(2)-O(3) 114(5) C(45)-C(44)-C(43) 119.1(15) O(3')-Li(2)-Cl(4) 116(3) C(44)-C(45)-C(46) 119.3(15) O(4')-Li(2)-Cl(4) 115.0(12) C(44)-C(45)-C(48) 117.5(18) O(3)-Li(2)-Cl(4) 112(5) C(46)-C(45)-C(48) 123.3(18) O(3')-Li(2)-Cl(5) 115(2) C(45)-C(46)-C(47) 119.4(14) O(4')-Li(2)-Cl(5) 110.2(11) C(42)-C(47)-C(46) 123.5(14) O(4)-Li(2)-Cl(5) 133(2) C(52)-O(3)-C(49) 89(5) O(3)-Li(2)-Cl(5) 110(3) C(52)-O(3)-Li(2) 126(5) Cl(4)-Li(2)-Cl(5) 94.7(8) C(49)-O(3)-Li(2) 121(7) O(3')-Li(2)-In(2) 118.0(15) O(3)-C(49)-C(50) 85(4) O(4')-Li(2)-In(2) 135.8(9) C(51)-C(50)-C(49) 88(3) O(4)-Li(2)-In(2) 100(2) C(50)-C(51)-C(52) 109(3) O(3)-Li(2)-In(2) 111.2(18) O(3)-C(52)-C(51) 102(5) Cl(4)-Li(2)-In(2) 48.7(4) C(52')-O(3')-C(49') 87(5) Cl(5)-Li(2)-In(2) 48.1(4) C(52')-O(3')-Li(2) 137(4) C(30)-C(29)-C(34) 119.3(13) C(49')-O(3')-Li(2) 120(3) C(30)-C(29)-In(2) 119.9(11) O(3')-C(49')-C(50') 84(4) C(34)-C(29)-In(2) 120.6(11) C(51')-C(50')-C(49') 89(2)
209
Table 21 (con’t). Bond angles [°] for [R InCl3][Li(OEt2)(THF)] (7)
Atoms Distance Atoms Distance C(50')-C(51')-C(52') 108(2) C(56)-C(55)-C(54) 115(3) O(3')-C(52')-C(51') 99(4) C(55)-C(56)-O(4) 94(3) C(53)-O(4)-C(56) 113(3) C(53')-O(4')-C(56') 116.3(16) C(32)-C(31)-C(30) 119.8(15) C(53')-O(4')-Li(2) 118.4(15) C(31)-C(32)-C(33) 123.1(15) C(56')-O(4')-Li(2) 122.4(14) C(53)-O(4)-Li(2) 102(5) C(54')-C(53')-O(4') 110(2) C(56)-O(4)-Li(2) 127(5) C(53')-C(54')-C(55') 101(2) C(54)-C(53)-O(4) 108(3) C(56')-C(55')-C(54') 116(2) C(53)-C(54)-C(55) 100(3) C(55')-C(56')-O(4') 96(2)
210
Structural Data for R 3In (8) (R = 2,6-(4-Me-C6H4)2C6H3-)
Table 22. Crystal data and structural refinement for R 3In (8)
Empirical formula C60H51In Formula weight 886.83 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/n Unit cell dimensions a = 11.6715(4) Å b = 19.3972(7) Å c = 21.2111(7) Å = 90°
= 103.10°
= 90°
Volume 4677.1(3) A3 Z, Calculated density 4, 1.259 Mg/m3 Absorption coefficient 0.543 mm-1 F(000) 1840 Crystal size 0.26 x 0.18 x 0.14 mm Theta range for data collection 2.08 to 28.30 deg. Limiting indices -15<=h<=15, -22<=k<=25, -27<=l<=28 Reflections collected / unique 37381 / 11290 [R(int) = 0.0183] Completeness to theta 28.30 97.1 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9278 and 0.8717 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 11290 / 0 / 550 Goodness-of-fit on F^2 1.003 Final R indices [I>2sigma(I)] R1 = 0.0277, wR2 = 0.0741 R indices (all data) R1 = 0.0376, wR2 = 0.0801 Largest diff. peak and hole 0.319 and -0.536 e.Å-3
211
Table 23. Bond Lengths [Å] for R 3In (8)
Atoms Distance Atoms Distance
In(1)-C(41) 2.1868(17) C(27)-C(32) 1.389(2)
In(1)-C(21) 2.2019(16) C(28)-C(29) 1.380(3)
In(1)-C(1) 2.2043(16) C(29)-C(30) 1.380(3)
C(1)-C(6) 1.406(2) C(30)-C(31) 1.382(3)
C(1)-C(2) 1.409(2) C(30)-C(33) 1.515(3)
C(2)-C(3) 1.399(3) C(31)-C(32) 1.385(3)
C(2)-C(14) 1.490(2) C(34)-C(39) 1.400(3)
C(3)-C(4) 1.375(3) C(34)-C(35) 1.384(3)
C(4)-C(5) 1.382(3) C(35)-C(36) 1.383(3)
C(5)-C(6) 1.397(2) C(36)-C(37) 1.376(4)
C(6)-C(7) 1.489(2) C(37)-C(38) 1.386(4)
C(7)-C(12) 1.388(3) C(37)-C(40) 1.513(3)
C(7)-C(8) 1.387(3) C(38)-C(39) 1.387(3)
C(8)-C(9) 1.383(3) C(41)-C(46) 1.404(3)
C(9)-C(10) 1.374(3) C(41)-C(42) 1.412(3)
C(10)-C(11) 1.376(3) C(42)-C(43) 1.394(3)
C(10)-C(13) 1.517(3) C(42)-C(54) 1.490(3)
C(11)-C(12) 1.386(3) C(43)-C(44) 1.376(4)
C(14)-C(15) 1.388(3) C(44)-C(45) 1.365(4)
C(14)-C(19) 1.388(3) C(45)-C(46) 1.401(3)
C(15)-C(16) 1.384(3) C(46)-C(47) 1.485(3)
C(16)-C(17) 1.376(3) C(47)-C(52) 1.385(3)
C(17)-C(18) 1.377(3) C(47)-C(48) 1.386(3)
C(17)-C(20) 1.512(3) C(48)-C(49) 1.381(4)
C(18)-C(19) 1.388(3) C(49)-C(50) 1.381(4)
C(21)-C(26) 1.409(2) C(50)-C(51) 1.370(4)
C(21)-C(22) 1.409(2) C(50)-C(53) 1.517(4)
C(22)-C(23) 1.395(3) C(51)-C(52) 1.378(4)
C(22)-C(34) 1.491(3) C(54)-C(59) 1.376(3)
C(23)-C(24) 1.376(3) C(54)-C(55) 1.380(3)
C(24)-C(25) 1.374(3) C(55)-C(56) 1.396(4)
C(25)-C(26) 1.401(2) C(56)-C(57) 1.361(4)
C(26)-C(27) 1.480(2) C(57)-C(58) 1.361(4)
C(27)-C(28) 1.391(2) C(57)-C(60) 1.525(4)
C(58)-C(59) 1.388(3)
212
Table 24. Bond angles [°] for R 3In (8)
Atoms Angle Atoms Angle
C(41)-In(1)-C(21) 123.52(6) C(15)-C(14)-C(19) 117.55(19)
C(41)-In(1)-C(1) 123.80(6) C(15)-C(14)-C(2) 122.52(18)
C(21)-In(1)-C(1) 112.66(6) C(19)-C(14)-C(2) 119.83(17)
C(6)-C(1)-C(2) 117.85(15) C(14)-C(15)-C(16) 120.6(2)
C(6)-C(1)-In(1) 118.45(11) C(17)-C(16)-C(15) 121.8(2)
C(2)-C(1)-In(1) 122.52(12) C(16)-C(17)-C(18) 117.8(2)
C(1)-C(2)-C(3) 119.86(17) C(16)-C(17)-C(20) 121.4(2)
C(1)-C(2)-C(14) 122.69(15) C(18)-C(17)-C(20) 120.8(3)
C(3)-C(2)-C(14) 117.41(16) C(19)-C(18)-C(17) 121.1(2)
C(4)-C(3)-C(2) 121.42(17) C(18)-C(19)-C(14) 121.1(2)
C(3)-C(4)-C(5) 119.53(17) C(26)-C(21)-C(22) 117.56(15)
C(6)-C(5)-C(4) 120.23(18) C(26)-C(21)-In(1) 118.34(11)
C(1)-C(6)-C(5) 121.04(16) C(22)-C(21)-In(1) 123.02(13)
C(1)-C(6)-C(7) 121.07(15) C(23)-C(22)-C(21) 120.26(18)
C(5)-C(6)-C(7) 117.88(16) C(23)-C(22)-C(34) 117.12(16)
C(12)-C(7)-C(8) 117.79(17) C(21)-C(22)-C(34) 122.58(16)
C(12)-C(7)-C(6) 120.50(17) C(24)-C(23)-C(22) 121.34(18)
C(8)-C(7)-C(6) 121.71(17) C(23)-C(24)-C(25) 119.41(18)
C(9)-C(8)-C(7) 120.9(2) C(24)-C(25)-C(26) 120.70(18)
C(10)-C(9)-C(8) 121.3(2) C(21)-C(26)-C(25) 120.68(16)
C(11)-C(10)-C(9) 117.91(19) C(21)-C(26)-C(27) 121.31(14)
C(11)-C(10)-C(13) 121.5(3) C(25)-C(26)-C(27) 118.01(16)
C(9)-C(10)-C(13) 120.6(2) C(28)-C(27)-C(32) 117.00(17)
C(10)-C(11)-C(12) 121.6(2) C(28)-C(27)-C(26) 121.99(16)
C(7)-C(12)-C(11) 120.4(2) C(32)-C(27)-C(26) 121.01(16)
213
Table 24 (con’t). Bond angles [°] for R 3In (8)
Atoms Angle Atoms Angle
C(27)-C(28)-C(29) 121.28(19) C(45)-C(44)-C(43) 119.9(2)
C(30)-C(29)-C(28) 121.8(2) C(44)-C(45)-C(46) 121.2(2)
C(31)-C(30)-C(29) 116.99(19) C(41)-C(46)-C(45) 119.9(2)
C(31)-C(30)-C(33) 121.2(2) C(41)-C(46)-C(47) 122.31(18)
C(29)-C(30)-C(33) 121.8(2) C(45)-C(46)-C(47) 117.72(19)
C(30)-C(31)-C(32) 121.82(19) C(52)-C(47)-C(48) 117.0(2)
C(27)-C(32)-C(31) 120.97(18) C(52)-C(47)-C(46) 122.6(2)
C(39)-C(34)-C(35) 117.79(19) C(48)-C(47)-C(46) 120.33(19)
C(39)-C(34)-C(22) 121.2(2) C(49)-C(48)-C(47) 120.9(2)
C(35)-C(34)-C(22) 120.89(18) C(50)-C(49)-C(48) 121.8(3)
C(34)-C(35)-C(36) 121.5(2) C(49)-C(50)-C(51) 117.0(3)
C(37)-C(36)-C(35) 121.0(3) C(49)-C(50)-C(53) 121.2(3)
C(36)-C(37)-C(38) 118.1(2) C(51)-C(50)-C(53) 121.7(3)
C(36)-C(37)-C(40) 121.8(3) C(52)-C(51)-C(50) 121.7(3)
C(38)-C(37)-C(40) 120.1(3) C(51)-C(52)-C(47) 121.4(3)
C(39)-C(38)-C(37) 121.6(2) C(59)-C(54)-C(55) 116.9(2)
C(34)-C(39)-C(38) 120.0(2) C(59)-C(54)-C(42) 121.19(18)
C(46)-C(41)-C(42) 118.03(17) C(55)-C(54)-C(42) 121.7(2)
C(46)-C(41)-In(1) 120.43(14) C(54)-C(55)-C(56) 120.6(2)
C(42)-C(41)-In(1) 121.53(13) C(57)-C(56)-C(55) 122.0(3)
C(43)-C(42)-C(41) 120.3(2) C(58)-C(57)-C(56) 117.4(2)
C(43)-C(42)-C(54) 116.92(19) C(58)-C(57)-C(60) 121.9(3)
C(41)-C(42)-C(54) 122.70(17) C(56)-C(57)-C(60) 120.7(3)
C(42)-C(43)-C(44) 120.6(2) C(57)-C(58)-C(59) 121.6(2)
C(54)-C(59)-C(58) 121.4(2)
214
Structural Data for [R3Ga3]Na3 (9) (R =2,6-(4-t-BuC6H4)2C6H3-)
Table 25. Crystal data and structural refinement for [R3Ga3]Na3 (9) Empirical formula C90H114Ga3Na3O3 Formula weight 1521.94 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/c Unit cell dimensions a = 16.760(3) Å b = 17.875(4) Å c = 29.598(6) Å = 90°
= 103.970(5)°
= 90°
Volume 8605(3) Å3 Z, Calculated density 4, 1.175 Mg/m3 Absorption coefficient 0.993 mm-1 F(000) 3216 Crystal size 0.50 x 0.40 x 0.30 mm Theta range for data collection 1.25 to 25.00 deg. Limiting indices -19<=h<=18, -9<=k<=19, -35<=l<=35 Reflections collected / unique 29576 / 13108 [R(int) = 0.0674] Completeness to theta = 25.00 86.6 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 13108 / 0 / 854 Goodness-of-fit on F^2 1 Final R indices [I>2sigma(I)] R1 = 0.0694, wR2 = 0.1355 R indices (all data) R1 = 0.1446, wR2 = 0.1645 Largest diff. peak and hole 0.516 and -0.321 e.Å-3
215
Table 26. Bond Lengths [Å] for [R3Ga3]Na3 (9) Atoms Distance Atoms Distance Ga(1)-C(8) 2.040(6) Na(2)-C(1) 3.107(8) Ga(1)-C(1) 2.034(6) Na(3)-O(3) 2.245(9) Ga(1)-Ga(2) 2.4863(10) Na(3)-O(2) 2.332(9) Ga(1)-Ga(3) 2.5251(10) Na(3)-C(27) 2.644(5) Ga(1)-Na(2) 2.964(4) Na(3)-C(86') 3.10(3) Ga(1)-Na(1) 3.057(3) Na(3)-C(32) 3.086(7) Ga(2)-C(33) 2.024(7) Na(3)-C(83) 3.08(3) Ga(2)-C(27) 2.064(6) C(1)-C(6) 1.414(8) Ga(2)-Na(3) 2.978(3) C(1)-C(2) 1.409(9) Ga(2)-Na(1) 3.201(3) C(2)-C(3) 1.400(9) Ga(3)-C(64) 2.027(6) C(2)-C(7) 1.513(9) Ga(3)-C(53) 2.044(6) C(3)-C(4) 1.346(10) Ga(3)-Na(1) 3.019(3) C(4)-C(5) 1.386(10) Ga(3)-Na(2) 3.145(4) C(5)-C(6) 1.386(9) Na(1)-C(33) 2.647(6) C(6)-C(17) 1.493(9) Na(1)-C(34) 2.807(7) C(7)-C(8) 1.391(8) Na(1)-C(19) 2.846(7) C(7)-C(12) 1.397(9) Na(1)-C(18) 2.916(7) C(8)-C(9) 1.384(8) Na(1)-C(20) 2.921(7) C(9)-C(10) 1.383(9) Na(1)-C(21) 2.945(8) C(10)-C(11) 1.384(10) Na(1)-C(17) 3.023(7) C(10)-C(13) 1.572(11) Na(1)-C(22) 3.007(8) C(11)-C(12) 1.370(10) Na(2)-O(1) 2.250(8) C(13)-C(14) 1.455(12) Na(2)-C(8) 2.701(7) C(13)-C(15) 1.470(13) Na(2)-C(53) 2.741(7) C(13)-C(16) 1.561(15) Na(2)-C(58) 2.887(7) C(17)-C(22) 1.359(9) Na(2)-C(7) 2.920(7) C(17)-C(18) 1.382(10)
216
Table 26 (con’t). Bond Lengths [Å] for [R3Ga3]Na3 (9) Atoms Distance Atoms Distance C(18)-C(19) 1.394(10) C(36)-C(37) 1.379(10) C(19)-C(20) 1.374(10) C(37)-C(38) 1.422(9) C(20)-C(21) 1.375(11) C(39)-C(42) 1.438(12) C(20)-C(23) 1.534(11) C(39)-C(40) 1.515(11) C(21)-C(22) 1.387(10) C(39)-C(41) 1.540(15) C(23)-C(25) 1.46(2) C(43)-C(44) 1.350(9) C(23)-C(24') 1.52(2) C(43)-C(48) 1.397(9) C(23)-C(26') 1.60(3) C(44)-C(45) 1.379(9) C(23)-C(24) 1.56(2) C(45)-C(46) 1.388(9) C(23)-C(25') 1.64(3) C(46)-C(47) 1.354(10) C(23)-C(26) 1.76(3) C(46)-C(49) 1.537(10) C(24)-C(24') 1.02(2) C(47)-C(48) 1.368(10) C(24')-C(26) 1.90(3) C(49)-C(52) 1.524(11) C(25)-C(25') 1.13(3) C(49)-C(51) 1.492(13) C(25)-C(26') 1.47(3) C(49)-C(50) 1.505(13) C(26)-C(26') 1.29(3) C(53)-C(58) 1.392(8) C(27)-C(28) 1.424(8) C(53)-C(54) 1.432(8) C(27)-C(32) 1.429(8) C(54)-C(55) 1.393(9) C(28)-C(29) 1.370(9) C(54)-C(59) 1.489(9) C(28)-C(38) 1.484(9) C(55)-C(56) 1.371(10) C(29)-C(30) 1.378(11) C(56)-C(57) 1.389(10) C(30)-C(31) 1.365(10) C(57)-C(58) 1.418(9) C(31)-C(32) 1.415(9) C(58)-C(69) 1.467(9) C(32)-C(43) 1.516(9) C(59)-C(64) 1.391(9) C(33)-C(38) 1.407(8) C(59)-C(60) 1.385(9) C(33)-C(34) 1.401(9) C(60)-C(61) 1.365(10) C(34)-C(35) 1.412(9) C(61)-C(62) 1.394(10) C(35)-C(36) 1.361(10) C(62)-C(63) 1.405(8) C(35)-C(39) 1.525(10) C(62)-C(65) 1.513(10)
217
Table 26 (con’t). Bond Lengths [Å] for [R3Ga3]Na3 (9) Atoms Distance Atoms Distance C(63)-C(64) 1.389(8) C(79)-C(79') 0.99(5) C(65)-C(67) 1.500(10) C(79)-C(80) 1.31(4) C(65)-C(68) 1.493(11) C(79')-C(80) 0.82(5) C(65)-C(66) 1.536(10) C(81)-C(82) 1.37(2) C(69)-C(70) 1.411(10) O(2)-C(85) 1.66(2) C(69)-C(74) 1.406(10) O(2)-C(84) 1.483(16) C(70)-C(71) 1.361(12) C(83)-C(84) 1.58(3) C(71)-C(72) 1.364(12) C(83')-C(84) 1.48(4) C(72)-C(73) 1.415(12) C(85)-C(86') 1.33(3) C(72)-C(75) 1.553(12) C(85)-C(86) 1.33(4) C(73)-C(74) 1.366(10) C(86')-C(86) 0.79(4) C(75)-C(76') 1.48(3) O(3)-C(88') 1.44(5) C(75)-C(78') 1.56(4) O(3)-C(89') 1.38(4) C(75)-C(77') 1.61(4) O(3)-C(89) 1.67(6) C(75)-C(76) 1.53(3) O(3)-C(88) 1.73(4) C(75)-C(77) 1.61(2) C(87)-C(88') 1.18(5) C(75)-C(78) 1.69(2) C(87)-C(88) 1.38(4) C(76)-C(76') 1.30(3) C(87')-C(88') 1.69(9) C(76)-C(77') 1.60(4) C(87')-C(88) 1.75(8) C(76')-C(78) 2.01(3) C(88)-C(88') 1.18(5) C(77)-C(78') 1.16(4) C(89)-C(90') 1.11(6) C(77)-C(77') 1.42(4) C(89)-C(89') 1.40(6) C(78)-C(78') 1.54(4) C(89)-C(90) 1.79(6) O(1)-C(80) 1.42(3) C(89')-C(90') 1.33(5) O(1)-C(81) 1.34(2) C(89')-C(90) 1.21(4) C(90)-C(90') 0.99(4)
218
Table 27. Bond angles [°] for [R3Ga3]Na3 (9) Atoms Angle Atoms Angle C(8)-Ga(1)-C(1) 84.9(3) C(33)-Na(1)-C(20) 118.9(3) C(8)-Ga(1)-Ga(2) 112.12(17) C(34)-Na(1)-C(20) 125.0(2) C(1)-Ga(1)-Ga(2) 113.37(17) C(19)-Na(1)-C(20) 27.5(2) C(8)-Ga(1)-Ga(3) 109.78(19) C(18)-Na(1)-C(20) 48.9(2) C(1)-Ga(1)-Ga(3) 126.47(17) C(33)-Na(1)-C(21) 98.3(2) Ga(2)-Ga(1)-Ga(3) 107.79(3) C(34)-Na(1)-C(21) 115.8(2) C(8)-Ga(1)-Na(2) 62.13(19) C(19)-Na(1)-C(21) 47.5(2) C(1)-Ga(1)-Na(2) 74.3(2) C(18)-Na(1)-C(21) 55.2(2) Ga(2)-Ga(1)-Na(2) 170.70(11) C(20)-Na(1)-C(21) 27.1(2) Ga(3)-Ga(1)-Na(2) 69.37(7) C(33)-Na(1)-Ga(3) 101.86(15) C(8)-Ga(1)-Na(1) 174.3(2) C(34)-Na(1)-Ga(3) 92.45(16) C(1)-Ga(1)-Na(1) 99.4(2) C(19)-Na(1)-Ga(3) 111.6(2) Ga(2)-Ga(1)-Na(1) 69.67(5) C(18)-Na(1)-Ga(3) 95.81(19) Ga(3)-Ga(1)-Na(1) 64.66(6) C(20)-Na(1)-Ga(3) 139.0(2) Na(2)-Ga(1)-Na(1) 115.32(10) C(21)-Na(1)-Ga(3) 149.51(19) C(33)-Ga(2)-C(27) 85.4(3) C(33)-Na(1)-C(17) 116.2(2) C(33)-Ga(2)-Ga(1) 116.66(17) C(34)-Na(1)-C(17) 145.6(2) C(27)-Ga(2)-Ga(1) 124.93(15) C(19)-Na(1)-C(17) 48.5(2) C(33)-Ga(2)-Na(3) 91.54(18) C(18)-Na(1)-C(17) 26.83(19) C(27)-Ga(2)-Na(3) 60.03(15) C(20)-Na(1)-C(17) 56.8(2) Ga(1)-Ga(2)-Na(3) 151.04(9) C(21)-Na(1)-C(17) 47.3(2) C(33)-Ga(2)-Na(1) 55.51(16) Ga(3)-Na(1)-C(17) 102.75(16) C(27)-Ga(2)-Na(1) 102.55(16) C(33)-Na(1)-C(22) 97.5(2) Ga(1)-Ga(2)-Na(1) 63.59(5) C(34)-Na(1)-C(22) 124.2(2) Na(3)-Ga(2)-Na(1) 145.32(9) C(19)-Na(1)-C(22) 55.4(2) C(64)-Ga(3)-C(53) 86.9(3) C(18)-Na(1)-C(22) 46.5(2) C(64)-Ga(3)-Ga(1) 102.76(19) C(20)-Na(1)-C(22) 48.1(2) C(53)-Ga(3)-Ga(1) 120.65(17) C(21)-Na(1)-C(22) 26.9(2) C(64)-Ga(3)-Na(1) 125.9(2) Ga(3)-Na(1)-C(22) 126.46(19) C(53)-Ga(3)-Na(1) 145.78(18) C(17)-Na(1)-C(22) 26.05(18) Ga(1)-Ga(3)-Na(1) 66.24(6) C(33)-Na(1)-Ga(1) 84.47(15) C(64)-Ga(3)-Na(2) 107.3(2) C(34)-Na(1)-Ga(1) 99.24(15) C(53)-Ga(3)-Na(2) 59.36(18) C(19)-Na(1)-Ga(1) 110.5(2) Ga(1)-Ga(3)-Na(2) 61.91(7) C(18)-Na(1)-Ga(1) 82.72(19) Na(1)-Ga(3)-Na(2) 111.25(11) C(20)-Na(1)-Ga(1) 126.85(19) C(33)-Na(1)-C(34) 29.57(18) C(21)-Na(1)-Ga(1) 111.3(2) C(33)-Na(1)-C(19) 145.4(3) Ga(3)-Na(1)-Ga(1) 49.10(4) C(34)-Na(1)-C(19) 149.6(3) C(17)-Na(1)-Ga(1) 70.08(14) C(33)-Na(1)-C(18) 142.7(3) C(22)-Na(1)-Ga(1) 84.42(18) C(34)-Na(1)-C(18) 170.5(3) C(33)-Na(1)-Ga(2) 39.06(14) C(19)-Na(1)-C(18) 28.0(2) C(34)-Na(1)-Ga(2) 62.45(15)
219
Table 27 (con’t). Bond angles [°] for [R3Ga3]Na3 (9) Atoms Angle Atoms Angle C(19)-Na(1)-Ga(2) 137.2(2) C(27)-Na(3)-Ga(2) 42.57(14) C(18)-Na(1)-Ga(2) 114.2(2) O(3)-Na(3)-C(86') 101.3(6) C(20)-Na(1)-Ga(2) 128.2(2) O(2)-Na(3)-C(86') 44.9(6) C(21)-Na(1)-Ga(2) 101.1(2) C(27)-Na(3)-C(86') 116.6(6) Ga(3)-Na(1)-Ga(2) 81.16(6) Ga(2)-Na(3)-C(86') 92.8(5) C(17)-Na(1)-Ga(2) 89.36(15) O(3)-Na(3)-C(32) 116.0(3) C(22)-Na(1)-Ga(2) 83.69(16) O(2)-Na(3)-C(32) 117.7(2) Ga(1)-Na(1)-Ga(2) 46.74(4) C(27)-Na(3)-C(32) 27.52(17) O(1)-Na(2)-C(8) 115.8(3) Ga(2)-Na(3)-C(32) 63.94(14) O(1)-Na(2)-C(53) 125.4(3) C(86')-Na(3)-C(32) 142.7(6) C(8)-Na(2)-C(53) 109.2(2) O(3)-Na(3)-C(83) 99.7(7) O(1)-Na(2)-C(58) 101.1(3) O(2)-Na(3)-C(83) 49.3(6) C(8)-Na(2)-C(58) 137.7(2) C(27)-Na(3)-C(83) 87.9(6) C(53)-Na(2)-C(58) 28.49(17) Ga(2)-Na(3)-C(83) 126.3(5) O(1)-Na(2)-C(7) 91.8(3) C(86')-Na(3)-C(83) 94.2(8) C(8)-Na(2)-C(7) 28.31(17) C(32)-Na(3)-C(83) 79.4(6) C(53)-Na(2)-C(7) 137.4(2) C(6)-C(1)-C(2) 116.9(6) C(58)-Na(2)-C(7) 165.9(2) C(6)-C(1)-Ga(1) 130.9(5) O(1)-Na(2)-Ga(1) 146.3(3) C(2)-C(1)-Ga(1) 111.2(4) C(8)-Na(2)-Ga(1) 41.89(14) C(6)-C(1)-Na(2) 129.5(4) C(53)-Na(2)-Ga(1) 88.28(17) C(2)-C(1)-Na(2) 80.7(4) C(58)-Na(2)-Ga(1) 110.86(18) Ga(1)-C(1)-Na(2) 66.68(18) C(7)-Na(2)-Ga(1) 57.95(15) C(3)-C(2)-C(1) 120.4(7) O(1)-Na(2)-C(1) 110.5(3) C(3)-C(2)-C(7) 124.1(7) C(8)-Na(2)-C(1) 56.00(19) C(1)-C(2)-C(7) 115.4(6) C(53)-Na(2)-C(1) 119.8(2) C(4)-C(3)-C(2) 121.0(8) C(58)-Na(2)-C(1) 129.7(2) C(5)-C(4)-C(3) 120.7(8) C(7)-Na(2)-C(1) 48.25(19) C(6)-C(5)-C(4) 119.5(7) Ga(1)-Na(2)-C(1) 39.05(12) C(5)-C(6)-C(1) 121.5(7) O(1)-Na(2)-Ga(3) 164.2(2) C(5)-C(6)-C(17) 119.4(6) C(8)-Na(2)-Ga(3) 79.28(15) C(1)-C(6)-C(17) 119.0(6) C(53)-Na(2)-Ga(3) 39.90(14) C(8)-C(7)-C(12) 119.4(6) C(58)-Na(2)-Ga(3) 63.13(15) C(8)-C(7)-C(2) 117.0(6) C(7)-Na(2)-Ga(3) 104.01(17) C(12)-C(7)-C(2) 123.6(6) Ga(1)-Na(2)-Ga(3) 48.72(6) C(8)-C(7)-Na(2) 67.0(3) C(1)-Na(2)-Ga(3) 81.38(15) C(12)-C(7)-Na(2) 114.5(5) O(3)-Na(3)-O(2) 106.5(3) C(2)-C(7)-Na(2) 86.1(4) O(3)-Na(3)-C(27) 140.7(3) C(7)-C(8)-C(9) 118.7(6) O(2)-Na(3)-C(27) 107.5(3) C(7)-C(8)-Ga(1) 111.0(4) O(3)-Na(3)-Ga(2) 130.7(3) C(9)-C(8)-Ga(1) 130.3(5) O(2)-Na(3)-Ga(2) 116.3(2) C(7)-C(8)-Na(2) 84.6(4)
220
Table 27 (con’t). Bond angles [°] for [R3Ga3]Na3 (9) Atoms Angle Atoms Angle C(9)-C(8)-Na(2) 109.3(5) C(25)-C(23)-C(24) 122.4(14) Ga(1)-C(8)-Na(2) 76.0(2) C(24')-C(23)-C(24) 38.6(9) C(10)-C(9)-C(8) 123.1(6) C(26')-C(23)-C(24) 140.2(16) C(9)-C(10)-C(11) 116.4(7) C(25)-C(23)-C(25') 42.2(11) C(9)-C(10)-C(13) 122.7(7) C(24')-C(23)-C(25') 115.6(14) C(11)-C(10)-C(13) 120.8(7) C(26')-C(23)-C(25') 97.5(15) C(12)-C(11)-C(10) 122.8(7) C(24)-C(23)-C(25') 84.2(14) C(11)-C(12)-C(7) 119.5(7) C(25)-C(23)-C(20) 111.1(10) C(14)-C(13)-C(15) 116.5(10) C(24')-C(23)-C(20) 111.5(9) C(14)-C(13)-C(10) 113.5(7) C(26')-C(23)-C(20) 110.8(13) C(15)-C(13)-C(10) 109.1(9) C(24)-C(23)-C(20) 105.6(9) C(14)-C(13)-C(16) 105.5(11) C(25')-C(23)-C(20) 110.3(12) C(15)-C(13)-C(16) 101.8(10) C(25)-C(23)-C(26) 100.4(13) C(10)-C(13)-C(16) 109.5(8) C(24')-C(23)-C(26) 70.3(12) C(22)-C(17)-C(18) 117.2(8) C(26')-C(23)-C(26) 44.9(12) C(22)-C(17)-C(6) 121.9(7) C(24)-C(23)-C(26) 108.3(12) C(18)-C(17)-C(6) 120.8(7) C(25')-C(23)-C(26) 134.0(14) C(22)-C(17)-Na(1) 76.3(4) C(20)-C(23)-C(26) 108.4(11) C(18)-C(17)-Na(1) 72.3(4) C(24')-C(24)-C(23) 68.4(18) C(6)-C(17)-Na(1) 119.8(4) C(24)-C(24')-C(23) 73.0(18) C(17)-C(18)-C(19) 121.1(8) C(24)-C(24')-C(26) 133(2) C(17)-C(18)-Na(1) 80.9(4) C(23)-C(24')-C(26) 60.7(11) C(19)-C(18)-Na(1) 73.2(4) C(25')-C(25)-C(26') 139(3) C(20)-C(19)-C(18) 121.6(8) C(25')-C(25)-C(23) 77.2(19) C(20)-C(19)-Na(1) 79.3(4) C(26')-C(25)-C(23) 66.3(16) C(18)-C(19)-Na(1) 78.8(4) C(25)-C(25')-C(23) 60.5(18) C(21)-C(20)-C(19) 116.3(8) C(26')-C(26)-C(23) 61.2(19) C(21)-C(20)-C(23) 122.3(9) C(26')-C(26)-C(24') 105(2) C(19)-C(20)-C(23) 121.2(9) C(23)-C(26)-C(24') 48.9(10) C(21)-C(20)-Na(1) 77.4(4) C(25)-C(26')-C(26) 128(3) C(19)-C(20)-Na(1) 73.2(4) C(25)-C(26')-C(23) 56.6(15) C(23)-C(20)-Na(1) 115.0(5) C(26)-C(26')-C(23) 74(2) C(20)-C(21)-C(22) 122.2(8) C(28)-C(27)-C(32) 117.4(6) C(20)-C(21)-Na(1) 75.5(4) C(28)-C(27)-Ga(2) 109.6(4) C(22)-C(21)-Na(1) 79.0(4) C(32)-C(27)-Ga(2) 132.9(5) C(17)-C(22)-C(21) 121.4(8) C(28)-C(27)-Na(3) 104.7(4) C(17)-C(22)-Na(1) 77.6(4) C(32)-C(27)-Na(3) 93.7(3) C(21)-C(22)-Na(1) 74.0(4) Ga(2)-C(27)-Na(3) 77.40(18) C(25)-C(23)-C(24') 137.1(13) C(29)-C(28)-C(27) 121.1(7) C(25)-C(23)-C(26') 57.1(13) C(29)-C(28)-C(38) 123.1(7) C(24')-C(23)-C(26') 110.3(16) C(27)-C(28)-C(38) 115.8(6)
221
Table 27 (con’t). Bond angles [°] for [R3Ga3]Na3 (9) Atoms Angle Atoms Angle C(67)-C(65)-C(66) 107.0(7) C(77')-C(77)-C(75) 63.9(19) C(68)-C(65)-C(66) 107.6(7) C(77)-C(77')-C(76) 116(3) C(70)-C(69)-C(74) 115.0(7) C(77)-C(77')-C(75) 64(2) C(70)-C(69)-C(58) 122.9(8) C(76)-C(77')-C(75) 57.2(18) C(74)-C(69)-C(58) 122.1(6) C(78')-C(78)-C(75) 57.5(18) C(69)-C(70)-C(71) 122.0(9) C(78')-C(78)-C(76') 90(2) C(72)-C(71)-C(70) 122.9(9) C(75)-C(78)-C(76') 46.2(10) C(71)-C(72)-C(73) 116.5(8) C(77)-C(78')-C(75) 71(2) C(71)-C(72)-C(75) 122.6(10) C(77)-C(78')-C(78) 134(4) C(73)-C(72)-C(75) 120.9(10) C(75)-C(78')-C(78) 66.1(19) C(72)-C(73)-C(74) 121.1(9) C(80)-O(1)-C(81) 108.6(16) C(69)-C(74)-C(73) 122.4(8) C(80)-O(1)-Na(2) 122.0(14) C(76')-C(75)-C(78') 113(2) C(81)-O(1)-Na(2) 122.1(11) C(76')-C(75)-C(72) 115.6(11) C(79')-C(79)-C(80) 39(3) C(78')-C(75)-C(72) 120.1(18) C(80)-C(79')-C(79) 92(6) C(76')-C(75)-C(77') 109(2) C(79')-C(80)-O(1) 111(5) C(78')-C(75)-C(77') 90(2) C(79')-C(80)-C(79) 49(4) C(72)-C(75)-C(77') 104.7(15) O(1)-C(80)-C(79) 113(3) C(76')-C(75)-C(76) 50.8(12) C(82)-C(81)-O(1) 115.7(19) C(78')-C(75)-C(76) 125.1(18) C(85)-O(2)-C(84) 112.5(12) C(72)-C(75)-C(76) 112.3(12) C(85)-O(2)-Na(3) 119.5(8) C(77')-C(75)-C(76) 61.1(17) C(84)-O(2)-Na(3) 119.8(9) C(76')-C(75)-C(77) 138.7(13) C(84)-C(83)-Na(3) 84.8(15) C(78')-C(75)-C(77) 42.9(15) C(83')-C(84)-C(83) 123(2) C(72)-C(75)-C(77) 105.3(10) C(83')-C(84)-O(2) 113.4(19) C(77')-C(75)-C(77) 52.4(15) C(83)-C(84)-O(2) 100.4(16) C(76)-C(75)-C(77) 109.2(14) O(2)-C(85)-C(86') 93.6(19) C(76')-C(75)-C(78) 78.3(14) O(2)-C(85)-C(86) 124(2) C(78')-C(75)-C(78) 56.4(17) C(86')-C(85)-C(86) 34.4(19) C(72)-C(75)-C(78) 102.7(11) C(86)-C(86')-C(85) 73(4) C(77')-C(75)-C(78) 144.2(17) C(86)-C(86')-Na(3) 134(4) C(76)-C(75)-C(78) 126.6(15) C(85)-C(86')-Na(3) 94.2(18) C(77)-C(75)-C(78) 98.2(13) C(86')-C(86)-C(85) 73(4) C(76')-C(76)-C(77') 121(3) C(88')-O(3)-C(89') 90(3) C(76')-C(76)-C(75) 62.6(16) C(88')-O(3)-C(89) 107(3) C(77')-C(76)-C(75) 61.7(18) C(89')-O(3)-C(89) 54(2) C(75)-C(76')-C(76) 66.6(18) C(88')-O(3)-C(88) 42(2) C(75)-C(76')-C(78) 55.5(12) C(89')-O(3)-C(88) 118(2) C(76)-C(76')-C(78) 120(2) C(89)-O(3)-C(88) 98(2) C(78')-C(77)-C(77') 120(3) C(88')-O(3)-Na(3) 124(2) C(78')-C(77)-C(75) 66(2) C(89')-O(3)-Na(3) 122.3(15)
222
Table 27 (con’t). Bond angles [°] for [R3Ga3]Na3 (9) Atoms Atoms Atoms Atoms C(28)-C(29)-C(30) 120.5(8) C(47)-C(48)-C(43) 121.2(7) C(29)-C(30)-C(31) 121.3(8) C(52)-C(49)-C(51) 110.4(10) C(30)-C(31)-C(32) 120.0(8) C(52)-C(49)-C(46) 111.7(6) C(31)-C(32)-C(27) 119.7(7) C(51)-C(49)-C(46) 108.8(7) C(31)-C(32)-C(43) 118.9(7) C(52)-C(49)-C(50) 103.2(8) C(27)-C(32)-C(43) 121.2(6) C(51)-C(49)-C(50) 111.3(10) C(31)-C(32)-Na(3) 121.0(4) C(46)-C(49)-C(50) 111.4(8) C(27)-C(32)-Na(3) 58.8(3) C(58)-C(53)-C(54) 118.9(6) C(43)-C(32)-Na(3) 87.5(3) C(58)-C(53)-Ga(3) 133.3(5) C(38)-C(33)-C(34) 118.2(6) C(54)-C(53)-Ga(3) 107.5(4) C(38)-C(33)-Ga(2) 110.3(5) C(58)-C(53)-Na(2) 81.6(4) C(34)-C(33)-Ga(2) 131.5(5) C(54)-C(53)-Na(2) 106.9(4) C(38)-C(33)-Na(1) 105.2(4) Ga(3)-C(53)-Na(2) 80.7(2) C(34)-C(33)-Na(1) 81.6(4) C(55)-C(54)-C(53) 118.9(6) Ga(2)-C(33)-Na(1) 85.4(2) C(55)-C(54)-C(59) 123.4(6) C(35)-C(34)-C(33) 123.8(7) C(53)-C(54)-C(59) 117.7(6) C(35)-C(34)-Na(1) 112.4(4) C(54)-C(55)-C(56) 121.2(7) C(33)-C(34)-Na(1) 68.8(3) C(55)-C(56)-C(57) 121.5(8) C(34)-C(35)-C(36) 115.3(7) C(56)-C(57)-C(58) 118.3(7) C(34)-C(35)-C(39) 120.4(7) C(53)-C(58)-C(57) 121.1(6) C(36)-C(35)-C(39) 124.3(7) C(53)-C(58)-C(69) 123.0(6) C(37)-C(36)-C(35) 124.6(7) C(57)-C(58)-C(69) 115.7(6) C(36)-C(37)-C(38) 119.4(7) C(53)-C(58)-Na(2) 69.9(4) C(33)-C(38)-C(37) 118.7(7) C(57)-C(58)-Na(2) 111.5(5) C(33)-C(38)-C(28) 118.3(6) C(69)-C(58)-Na(2) 94.0(4) C(37)-C(38)-C(28) 123.0(6) C(64)-C(59)-C(60) 118.9(7) C(42)-C(39)-C(40) 115.0(9) C(64)-C(59)-C(54) 117.6(5) C(42)-C(39)-C(35) 111.4(8) C(60)-C(59)-C(54) 123.5(7) C(40)-C(39)-C(35) 112.5(7) C(61)-C(60)-C(59) 121.3(7) C(42)-C(39)-C(41) 102.2(11) C(62)-C(61)-C(60) 122.4(7) C(40)-C(39)-C(41) 101.9(9) C(61)-C(62)-C(63) 115.1(7) C(35)-C(39)-C(41) 113.0(7) C(61)-C(62)-C(65) 124.5(7) C(44)-C(43)-C(48) 116.3(7) C(63)-C(62)-C(65) 120.3(7) C(44)-C(43)-C(32) 123.4(6) C(64)-C(63)-C(62) 123.7(7) C(48)-C(43)-C(32) 120.3(7) C(59)-C(64)-C(63) 118.5(6) C(45)-C(44)-C(43) 121.9(7) C(59)-C(64)-Ga(3) 109.6(4) C(46)-C(45)-C(44) 122.0(7) C(63)-C(64)-Ga(3) 131.2(5) C(47)-C(46)-C(45) 115.7(7) C(62)-C(65)-C(67) 108.7(6) C(47)-C(46)-C(49) 125.1(7) C(62)-C(65)-C(68) 111.1(6) C(45)-C(46)-C(49) 119.2(7) C(67)-C(65)-C(68) 109.5(8) C(48)-C(47)-C(46) 122.9(7) C(62)-C(65)-C(66) 112.9(7)
223
Table 27 (con’t). Bond angles [°] for [R3Ga3]Na3 (9) Atoms Angle Atoms Angle C(89)-O(3)-Na(3) 128.9(19) C(90')-C(89)-O(3) 111(5) C(88)-O(3)-Na(3) 117.4(12) C(89')-C(89)-O(3) 53(3) C(88')-C(87)-C(88) 54(3) C(90')-C(89)-C(90) 30(3) C(88')-C(87')-C(88) 40(2) C(89')-C(89)-C(90) 42(2) C(88')-C(88)-C(87') 67(4) O(3)-C(89)-C(90) 82(3) C(88')-C(88)-C(87) 54(3) C(90')-C(89')-C(90) 46(2) C(87')-C(88)-C(87) 18(4) C(90')-C(89')-O(3) 117(3) C(88')-C(88)-O(3) 56(3) C(90)-C(89')-O(3) 123(3) C(87')-C(88)-O(3) 96(3) C(90')-C(89')-C(89) 48(3) C(87)-C(88)-O(3) 95(2) C(90)-C(89')-C(89) 86(4) C(88)-C(88')-C(87') 73(5) O(3)-C(89')-C(89) 74(3) C(88)-C(88')-C(87) 71(4) C(90')-C(90)-C(89') 74(3) C(87')-C(88')-C(87) 13(4) C(90')-C(90)-C(89) 34(3) C(88)-C(88')-O(3) 82(4) C(89')-C(90)-C(89) 51(2) C(87')-C(88')-O(3) 111(4) C(90)-C(90')-C(89) 116(6) C(87)-C(88')-O(3) 123(5) C(90)-C(90')-C(89') 61(3) C(90')-C(89)-C(89') 63(4) C(89)-C(90')-C(89') 69(4)
224
Structural Data for Cp2Hf(GaR)2 (10) (R = 2,6-(2,4,6-i-PrC6H2)2C6H3-)
Table 28. Crystal data and structural refinement for Cp2Hf(GaR)2 (10) Empirical formula C86H118Ga2HfO Formula weight 1485.74 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Orthorhombic, Pbcn Unit cell dimensions a = 15.879(4) Å b = 17.556(4) Å c = 29.381(6) Å = 90°
= 90°
= 90°
Volume 8191(3) Å3 Z, Calculated density 4, 1.205 Mg/m3 Absorption coefficient 1.958 mm-1 F(000) 3104 Crystal size 0.20 x 0.10 x 0.05 mm Theta range for data collection 2.22 to 25.00 deg. Limiting indices -18<=h<=14, -20<=k<=20, -34<=l<=34 Reflections collected / unique 41723 / 7217 [R(int) = 0.1355] Completeness to theta = 25.00 99.90% Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9084 and 0.6955 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 7217 / 141 / 431 Goodness-of-fit on F^2 1.01 Final R indices [I>2sigma(I)] R1 = 0.0613, wR2 = 0.1555 R indices (all data) R1 = 0.1600, wR2 = 0.2302 Largest diff. peak and hole 0.981 and -2.308 e.Å-3
225
Table 29. Bond Lengths [Å] for Cp2Hf(GaR)2 (10) Atoms Distance Atoms Distance Hf(1)-C(41')#1 2.40(5) C(16)-C(17) 1.40(2) Hf(1)-C(37)#1 2.44(4) C(19)-C(21) 1.53(2) Hf(1)-C(37')#1 2.48(4) C(19)-C(20) 1.515(19) Hf(1)-C(40)#1 2.49(5) C(22)-C(27) 1.379(15) Hf(1)-C(38)#1 2.48(3) C(22)-C(23) 1.393(17) Hf(1)-C(38')#1 2.50(4) C(23)-C(24) 1.381(18) Hf(1)-C(40')#1 2.48(6) C(23)-C(34) 1.53(2) Hf(1)-C(39)#1 2.49(5) C(24)-C(25) 1.357(19) Hf(1)-C(41)#1 2.48(5) C(25)-C(26) 1.338(19) Hf(1)-C(39')#1 2.51(5) C(25)-C(31) 1.577(19) Hf(1)-Ga(1) 2.6198(13) C(26)-C(27) 1.388(16) Hf(1)-Ga(1)#1 2.6198(13) C(27)-C(28) 1.513(18) Ga(1)-C(1) 2.021(10) C(28)-C(30) 1.51(2) C(1)-C(2) 1.396(14) C(28)-C(29) 1.53(2) C(1)-C(6) 1.409(14) C(31)-C(33) 1.43(3) C(2)-C(3) 1.357(15) C(31)-C(32) 1.51(3) C(2)-C(22) 1.526(15) C(34)-C(36) 1.50(2) C(3)-C(4) 1.427(16) C(34)-C(35) 1.54(2) C(4)-C(5) 1.372(15) C(37)-C(41) 1.40(5) C(5)-C(6) 1.400(14) C(37)-C(38) 1.42(3) C(6)-C(7) 1.501(15) C(38)-C(39) 1.43(5) C(7)-C(12) 1.374(16) C(39)-C(40) 1.36(5) C(7)-C(8) 1.395(16) C(40)-C(41) 1.37(6) C(8)-C(9) 1.417(17) C(37')-C(41') 1.41(4) C(8)-C(19) 1.505(18) C(37')-C(38') 1.48(6) C(9)-C(10) 1.336(18) C(38')-C(39') 1.40(5) C(10)-C(11) 1.364(18) C(39')-C(40') 1.36(5) C(10)-C(16) 1.554(18) C(40')-C(41') 1.42(6) C(11)-C(12) 1.399(16) O(1)-C(42')#2 1.36788(18) C(12)-C(13) 1.489(17) O(1)-C(42') 1.36789(17) C(13)-C(14) 1.529(17) O(1)-C(42)#2 1.3869(2) C(13)-C(15) 1.527(17) O(1)-C(42) 1.3869(2) C(16)-C(18) 1.37(2) C(42)-C(43) 1.3313(2) C(42')-C(43') 1.3691(2)
226
Table 30. Bond angles [°] for Cp2Hf(GaR)2 (10) Atoms Angle Atoms Angle C(41')#1-Hf(1)-C(37)#1 20.2(12) C(37')#1-Hf(1)-C(39')#1 55.5(16) C(41')#1-Hf(1)-C(37')#1 33.6(10) C(40)#1-Hf(1)-C(39')#1 19.3(11) C(37)#1-Hf(1)-C(37')#1 15.8(10) C(38)#1-Hf(1)-C(39')#1 47.0(12) C(41')#1-Hf(1)-C(40)#1 41.7(15) C(38')#1-Hf(1)-C(39')#1 32.3(11) C(37)#1-Hf(1)-C(40)#1 53.8(17) C(40')#1-Hf(1)-C(39')#1 31.6(11) C(37')#1-Hf(1)-C(40)#1 56.0(17) C(39)#1-Hf(1)-C(39')#1 15.5(10) C(41')#1-Hf(1)-C(38)#1 47.8(14) C(41)#1-Hf(1)-C(39')#1 48.1(14) C(37)#1-Hf(1)-C(38)#1 33.5(8) C(41')#1-Hf(1)-Ga(1) 130.8(12) C(37')#1-Hf(1)-C(38)#1 18.5(10) C(37)#1-Hf(1)-Ga(1) 122.2(12) C(40)#1-Hf(1)-C(38)#1 54.8(15) C(37')#1-Hf(1)-Ga(1) 107.1(15) C(41')#1-Hf(1)-C(38')#1 55.4(15) C(40)#1-Hf(1)-Ga(1) 98.1(12) C(37)#1-Hf(1)-C(38')#1 47.2(13) C(38)#1-Hf(1)-Ga(1) 88.8(13) C(37')#1-Hf(1)-C(38')#1 34.7(14) C(38')#1-Hf(1)-Ga(1) 76.4(13) C(40)#1-Hf(1)-C(38')#1 45.7(15) C(40')#1-Hf(1)-Ga(1) 110.3(14) C(38)#1-Hf(1)-C(38')#1 18.4(11) C(39)#1-Hf(1)-Ga(1) 76.2(11) C(41')#1-Hf(1)-C(40')#1 33.8(14) C(41)#1-Hf(1)-Ga(1) 128.3(13) C(37)#1-Hf(1)-C(40')#1 49.9(15) C(39')#1-Hf(1)-Ga(1) 80.4(13) C(37')#1-Hf(1)-C(40')#1 56.1(18) C(41')#1-Hf(1)-Ga(1)#1 96.8(14) C(40)#1-Hf(1)-C(40')#1 12.4(12) C(37)#1-Hf(1)-Ga(1)#1 117.0(13) C(38)#1-Hf(1)-C(40')#1 59.5(17) C(37')#1-Hf(1)-Ga(1)#1 128.9(13) C(38')#1-Hf(1)-C(40')#1 54.2(16) C(40)#1-Hf(1)-Ga(1)#1 78.5(13) C(41')#1-Hf(1)-C(39)#1 54.9(17) C(38)#1-Hf(1)-Ga(1)#1 133.2(10) C(37)#1-Hf(1)-C(39)#1 53.8(15) C(38')#1-Hf(1)-Ga(1)#1 121.6(15) C(37')#1-Hf(1)-C(39)#1 45.6(14) C(40')#1-Hf(1)-Ga(1)#1 74.4(14) C(40)#1-Hf(1)-C(39)#1 31.6(11) C(39)#1-Hf(1)-Ga(1)#1 104.7(14) C(38)#1-Hf(1)-C(39)#1 33.4(11) C(41)#1-Hf(1)-Ga(1)#1 84.7(12) C(38')#1-Hf(1)-C(39)#1 17.0(11) C(39')#1-Hf(1)-Ga(1)#1 89.2(14) C(40')#1-Hf(1)-C(39)#1 42.3(14) Ga(1)-Hf(1)-Ga(1)#1 100.76(6) C(41')#1-Hf(1)-C(41)#1 13.4(12) C(1)-Ga(1)-Hf(1) 171.7(3) C(37)#1-Hf(1)-C(41)#1 33.0(11) C(2)-C(1)-C(6) 117.9(9) C(37')#1-Hf(1)-C(41)#1 44.4(14) C(2)-C(1)-Ga(1) 120.5(8) C(40)#1-Hf(1)-C(41)#1 32.1(13) C(6)-C(1)-Ga(1) 121.4(8) C(38)#1-Hf(1)-C(41)#1 55.3(13) C(3)-C(2)-C(1) 122.5(10) C(38')#1-Hf(1)-C(41)#1 58.3(17) C(3)-C(2)-C(22) 117.9(10) C(40')#1-Hf(1)-C(41)#1 22.0(14) C(1)-C(2)-C(22) 119.4(10) C(39)#1-Hf(1)-C(41)#1 53.1(15) C(2)-C(3)-C(4) 119.7(11) C(41')#1-Hf(1)-C(39')#1 54.2(17) C(5)-C(4)-C(3) 118.8(11) C(37)#1-Hf(1)-C(39')#1 59.6(15) C(6)-C(5)-C(4) 121.3(11)
227
Table 30 (con’t). Bond angles [°] for Cp2Hf(GaR)2 (10) Atoms Angle Atoms Angle C(5)-C(6)-C(1) 119.8(10) C(26)-C(25)-C(24) 117.5(13) C(5)-C(6)-C(7) 117.0(10) C(26)-C(25)-C(31) 118.6(16) C(1)-C(6)-C(7) 123.1(10) C(24)-C(25)-C(31) 123.9(16) C(12)-C(7)-C(8) 120.9(11) C(25)-C(26)-C(27) 124.3(14) C(12)-C(7)-C(6) 120.9(11) C(22)-C(27)-C(26) 116.8(12) C(8)-C(7)-C(6) 118.2(11) C(22)-C(27)-C(28) 121.5(11) C(7)-C(8)-C(9) 117.0(13) C(26)-C(27)-C(28) 121.6(13) C(7)-C(8)-C(19) 122.5(12) C(27)-C(28)-C(30) 112.9(14) C(9)-C(8)-C(19) 120.2(13) C(27)-C(28)-C(29) 107.4(14) C(10)-C(9)-C(8) 123.7(13) C(30)-C(28)-C(29) 110.7(16) C(9)-C(10)-C(11) 116.9(12) C(33)-C(31)-C(32) 124(2) C(9)-C(10)-C(16) 120.4(16) C(33)-C(31)-C(25) 111.7(18) C(11)-C(10)-C(16) 122.7(15) C(32)-C(31)-C(25) 108.5(17) C(10)-C(11)-C(12) 123.8(13) C(36)-C(34)-C(23) 112.0(14) C(7)-C(12)-C(11) 117.6(12) C(36)-C(34)-C(35) 111.3(15) C(7)-C(12)-C(13) 123.1(12) C(23)-C(34)-C(35) 114.2(15) C(11)-C(12)-C(13) 119.3(13) C(41)-C(37)-C(38) 110(4) C(12)-C(13)-C(14) 113.1(12) C(37)-C(38)-C(39) 103(4) C(12)-C(13)-C(15) 115.2(12) C(40)-C(39)-C(38) 111(4) C(14)-C(13)-C(15) 105.8(12) C(39)-C(40)-C(41) 109(5) C(18)-C(16)-C(17) 125.5(18) C(40)-C(41)-C(37) 108(4) C(18)-C(16)-C(10) 114.5(15) C(41')-C(37')-C(38') 104(4) C(17)-C(16)-C(10) 112.9(14) C(39')-C(38')-C(37') 108(4) C(8)-C(19)-C(21) 111.3(14) C(40')-C(39')-C(38') 111(4) C(8)-C(19)-C(20) 112.1(13) C(39')-C(40')-C(41') 107(4) C(21)-C(19)-C(20) 110.7(14) C(37')-C(41')-C(40') 111(5) C(27)-C(22)-C(23) 120.9(12) C(42')#2-O(1)-C(42') 180 C(27)-C(22)-C(2) 120.5(10) C(42')#2-O(1)-C(42)#2 53.099(10) C(23)-C(22)-C(2) 118.5(11) C(42')-O(1)-C(42)#2 126.901(10) C(24)-C(23)-C(22) 117.8(14) C(42')#2-O(1)-C(42) 126.901(10) C(24)-C(23)-C(34) 118.9(14) C(42')-O(1)-C(42) 53.099(10) C(22)-C(23)-C(34) 123.0(13) C(42)#2-O(1)-C(42) 180 C(23)-C(24)-C(25) 122.7(14) C(43)-C(42)-O(1) 157.623(4) O(1)-C(42')-C(43') 117.031(11)
228
Structural Data for Cp2Hf(InR)2 (11) (R = 2,6-(2,4,6-i-PrC6H2)2C6H3-)
Table 31. Crystal data and structural refinement for Cp2Hf(InR)2 (11) Empirical formula C86H118HfIn2O Formula weight 1575.94 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Orthorhombic, Pbcn Unit cell dimensions a = 15.748(4) Å b = 17.855(5) Å c = 29.708(8) Å = 90°
= 90°
= 90°
Volume 8354(4) Å3 Z, Calculated density 4, 1.253 Mg/m3 Absorption coefficient 1.827 mm-1 F(000) 3248 Crystal size 0.07 x 0.07 x 0.06 mm Theta range for data collection 2.20 to 25.00 deg. Limiting indices -18<=h<=18, -21<=k<=21, -35<=l<=35 Reflections collected / unique 64198 / 7353 [R(int) = 0.2256] Completeness to theta = 25.00 99.90% Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.8983 and 0.8828 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 7353 / 75 / 413 Goodness-of-fit on F^2 1.008 Final R indices [I>2sigma(I)] R1 = 0.0653, wR2 = 0.1453 R indices (all data) R1 = 0.1888, wR2 = 0.2080 Largest diff. peak and hole 0.789 and -2.675 e.Å-3
229
Table 32. Bond Lengths [Å] for Cp2Hf(InR)2 (11)
Atoms Distance Atoms Distance
Hf(1)-C(37) 2.399(17) C(16)-C(17) 1.47(3)
Hf(1)-C(37)#1 2.399(17) C(16)-C(18) 1.53(3)
Hf(1)-C(38) 2.43(2) C(19)-C(21) 1.46(2)
Hf(1)-C(38)#1 2.43(2) C(19)-C(20) 1.52(2)
Hf(1)-C(41) 2.43(2) C(22)-C(23) 1.40(2)
Hf(1)-C(41)#1 2.43(2) C(22)-C(27) 1.41(2)
Hf(1)-C(39) 2.48(2) C(23)-C(24) 1.40(2)
Hf(1)-C(39)#1 2.48(2) C(23)-C(34) 1.50(2)
Hf(1)-C(40) 2.52(2) C(24)-C(25) 1.36(2)
Hf(1)-C(40)#1 2.52(2) C(25)-C(26) 1.34(2)
Hf(1)-In(1) 2.7667(10) C(25)-C(31) 1.58(2)
Hf(1)-In(1)#1 2.7667(10) C(25)-C(31') 1.60(4)
In(1)-C(1) 2.194(13) C(26)-C(27) 1.40(2)
C(1)-C(6) 1.403(17) C(27)-C(28) 1.49(2)
C(1)-C(2) 1.429(17) C(28)-C(29) 1.50(2)
C(2)-C(3) 1.374(17) C(28)-C(30) 1.52(2)
C(2)-C(22) 1.522(19) C(31)-C(33) 1.34(3)
C(3)-C(4) 1.357(17) C(31)-C(32) 1.39(3)
C(4)-C(5) 1.401(17) C(31')-C(33') 1.33(3)
C(5)-C(6) 1.338(18) C(31')-C(32') 1.38(3)
C(6)-C(7) 1.539(17) C(34)-C(35) 1.50(2)
C(7)-C(12) 1.364(18) C(34)-C(36) 1.51(2)
C(7)-C(8) 1.41(2) C(37)-C(41) 1.34(3)
C(8)-C(9) 1.38(2) C(37)-C(38) 1.38(3)
C(8)-C(19) 1.52(2) C(38)-C(39) 1.33(3)
C(9)-C(10) 1.40(2) C(39)-C(40) 1.34(3)
C(10)-C(11) 1.32(2) C(40)-C(41) 1.38(3)
C(10)-C(16) 1.52(2) O(1)-C(42')#2 1.3306(3)
C(11)-C(12) 1.39(2) O(1)-C(42') 1.3306(3)
C(12)-C(13) 1.52(2) O(1)-C(42)#2 1.5381(3)
C(13)-C(15) 1.53(2) O(1)-C(42) 1.5381(3)
C(13)-C(14) 1.56(2) C(42)-C(43) 1.5359(3)
C(42')-C(43') 1.2695(3)
230
Table 33. Bond angles [°] for Cp2Hf(InR)2 (11). Atoms Angle Atoms Angle C(37)-Hf(1)-C(37)#1 82.1(15) C(38)-Hf(1)-C(40)#1 132.6(11) C(37)-Hf(1)-C(38) 33.3(7) C(38)#1-Hf(1)-C(40)#1 52.7(9) C(37)#1-Hf(1)-C(38) 94.3(12) C(41)-Hf(1)-C(40)#1 154.1(10) C(37)-Hf(1)-C(38)#1 94.3(11) C(41)#1-Hf(1)-C(40)#1 32.3(8) C(37)#1-Hf(1)-C(38)#1 33.3(7) C(39)-Hf(1)-C(40)#1 149.1(8) C(38)-Hf(1)-C(38)#1 119(2) C(39)#1-Hf(1)-C(40)#1 31.0(7) C(37)-Hf(1)-C(41) 32.2(8) C(40)-Hf(1)-C(40)#1 172.0(14) C(37)#1-Hf(1)-C(41) 105.2(17) C(37)-Hf(1)-In(1) 125.8(7) C(38)-Hf(1)-C(41) 53.9(7) C(37)#1-Hf(1)-In(1) 115.6(9) C(38)#1-Hf(1)-C(41) 101.5(10) C(38)-Hf(1)-In(1) 92.6(8) C(37)-Hf(1)-C(41)#1 105.2(17) C(38)#1-Hf(1)-In(1) 129.3(7) C(37)#1-Hf(1)-C(41)#1 32.2(8) C(41)-Hf(1)-In(1) 129.1(9) C(38)-Hf(1)-C(41)#1 101.5(10) C(41)#1-Hf(1)-In(1) 83.7(10) C(38)#1-Hf(1)-C(41)#1 53.9(7) C(39)-Hf(1)-In(1) 78.5(7) C(41)-Hf(1)-C(41)#1 134(2) C(39)#1-Hf(1)-In(1) 102.4(9) C(37)-Hf(1)-C(39) 53.0(9) C(40)-Hf(1)-In(1) 97.8(11) C(37)#1-Hf(1)-C(39) 125.8(11) C(40)#1-Hf(1)-In(1) 76.7(7) C(38)-Hf(1)-C(39) 31.5(7) C(37)-Hf(1)-In(1)#1 115.6(9) C(38)#1-Hf(1)-C(39) 147.3(14) C(37)#1-Hf(1)-In(1)#1 125.8(7) C(41)-Hf(1)-C(39) 52.6(10) C(38)-Hf(1)-In(1)#1 129.3(7) C(41)#1-Hf(1)-C(39) 126.7(10) C(38)#1-Hf(1)-In(1)#1 92.6(8) C(37)-Hf(1)-C(39)#1 125.8(11) C(41)-Hf(1)-In(1)#1 83.7(10) C(37)#1-Hf(1)-C(39)#1 53.0(9) C(41)#1-Hf(1)-In(1)#1 129.1(9) C(38)-Hf(1)-C(39)#1 147.3(14) C(39)-Hf(1)-In(1)#1 102.4(9) C(38)#1-Hf(1)-C(39)#1 31.5(7) C(39)#1-Hf(1)-In(1)#1 78.5(7) C(41)-Hf(1)-C(39)#1 126.7(10) C(40)-Hf(1)-In(1)#1 76.7(7) C(41)#1-Hf(1)-C(39)#1 52.6(10) C(40)#1-Hf(1)-In(1)#1 97.8(11) C(39)-Hf(1)-C(39)#1 178.8(15) In(1)-Hf(1)-In(1)#1 95.26(4) C(37)-Hf(1)-C(40) 53.1(10) C(1)-In(1)-Hf(1) 171.3(3) C(37)#1-Hf(1)-C(40) 134.8(12) C(6)-C(1)-C(2) 117.1(12) C(38)-Hf(1)-C(40) 52.7(9) C(6)-C(1)-In(1) 121.0(10) C(38)#1-Hf(1)-C(40) 132.6(11) C(2)-C(1)-In(1) 121.9(10) C(41)-Hf(1)-C(40) 32.3(8) C(3)-C(2)-C(1) 121.1(14) C(41)#1-Hf(1)-C(40) 154.1(10) C(3)-C(2)-C(22) 118.8(12) C(39)-Hf(1)-C(40) 31.0(7) C(1)-C(2)-C(22) 120.1(12) C(39)#1-Hf(1)-C(40) 149.1(8) C(4)-C(3)-C(2) 118.6(13) C(37)-Hf(1)-C(40)#1 134.8(12) C(3)-C(4)-C(5) 122.0(13) C(37)#1-Hf(1)-C(40)#1 53.1(10) C(6)-C(5)-C(4) 119.6(13)
231
Table 33 (con’t). Bond angles [°] for Cp2Hf(InR)2 (11). Atoms Angle Atoms Angle C(5)-C(6)-C(1) 121.5(13) C(25)-C(26)-C(27) 123.1(17) C(5)-C(6)-C(7) 120.8(13) C(26)-C(27)-C(22) 116.5(17) C(1)-C(6)-C(7) 117.6(12) C(26)-C(27)-C(28) 121.2(16) C(12)-C(7)-C(8) 121.8(14) C(22)-C(27)-C(28) 122.0(16) C(12)-C(7)-C(6) 119.7(14) C(29)-C(28)-C(27) 113.7(15) C(8)-C(7)-C(6) 118.5(13) C(29)-C(28)-C(30) 108.8(15) C(9)-C(8)-C(7) 116.5(16) C(27)-C(28)-C(30) 112.7(15) C(9)-C(8)-C(19) 120.9(17) C(33)-C(31)-C(32) 127(4) C(7)-C(8)-C(19) 122.2(16) C(33)-C(31)-C(25) 121(4) C(8)-C(9)-C(10) 122.4(17) C(32)-C(31)-C(25) 111(4) C(11)-C(10)-C(9) 117.8(16) C(33')-C(31')-C(32') 129(3) C(11)-C(10)-C(16) 120.6(19) C(33')-C(31')-C(25) 115(3) C(9)-C(10)-C(16) 121.5(19) C(32')-C(31')-C(25) 115(3) C(10)-C(11)-C(12) 123.7(18) C(23)-C(34)-C(35) 114.3(15) C(7)-C(12)-C(11) 117.7(16) C(23)-C(34)-C(36) 108.4(15) C(7)-C(12)-C(13) 122.6(14) C(35)-C(34)-C(36) 111.0(15) C(11)-C(12)-C(13) 119.7(15) C(41)-C(37)-C(38) 108(3) C(12)-C(13)-C(15) 114.8(15) C(41)-C(37)-Hf(1) 75.2(14) C(12)-C(13)-C(14) 109.3(14) C(38)-C(37)-Hf(1) 74.5(12) C(15)-C(13)-C(14) 108.8(16) C(39)-C(38)-C(37) 107(3) C(17)-C(16)-C(10) 112(2) C(39)-C(38)-Hf(1) 76.3(15) C(17)-C(16)-C(18) 120(2) C(37)-C(38)-Hf(1) 72.2(12) C(10)-C(16)-C(18) 111(2) C(38)-C(39)-C(40) 111(3) C(21)-C(19)-C(8) 111.7(17) C(38)-C(39)-Hf(1) 72.2(15) C(21)-C(19)-C(20) 112.7(17) C(40)-C(39)-Hf(1) 76.0(17) C(8)-C(19)-C(20) 111.4(17) C(39)-C(40)-C(41) 107(3) C(23)-C(22)-C(27) 121.6(16) C(39)-C(40)-Hf(1) 72.9(17) C(23)-C(22)-C(2) 117.6(15) C(41)-C(40)-Hf(1) 70.5(15) C(27)-C(22)-C(2) 120.8(15) C(40)-C(41)-C(37) 108(3) C(22)-C(23)-C(24) 116.9(16) C(40)-C(41)-Hf(1) 77.2(16) C(22)-C(23)-C(34) 123.2(14) C(37)-C(41)-Hf(1) 72.6(13) C(24)-C(23)-C(34) 119.8(16) C(42')#2-O(1)-C(42') 180 C(25)-C(24)-C(23) 122.0(17) C(42')#2-O(1)-C(42)#2 47.487(9) C(26)-C(25)-C(24) 119.8(16) C(42')-O(1)-C(42)#2 132.513(9) C(26)-C(25)-C(31) 129(4) C(42')#2-O(1)-C(42) 132.513(9) C(24)-C(25)-C(31) 110(4) C(42')-O(1)-C(42) 47.487(9) C(26)-C(25)-C(31') 115(3) C(42)#2-O(1)-C(42) 180 C(24)-C(25)-C(31') 125(3) C(43)-C(42)-O(1) 131.438(10) C(31)-C(25)-C(31') 19(6) C(43')-C(42')-O(1) 137.392(3)
232
Structural Data for (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12) (R = 2,6-(4-t-BuC6H4)2C6H3-)
Table 34. Crystal data and structural refinement for (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12)
Empirical formula C53H55ClGaZr2 Formula weight 979.58
Temperature 100(2) K
Wavelength 1.54178 Å Crystal system, space group Monoclinic, P2(1)/c
Unit cell dimensions a = 17.9545(3) Å
b = 13.3890(3) Å c = 18.1881(5) Å
= 90°
= 99.2920(10)°
= 90°
Volume 4314.92(17) Å3 Z, Calculated density 4, 1.508 Mg/m3
Absorption coefficient 5.454 mm^-1
F(000) 2004
Crystal size 0.40 x 0.18 x 0.08 mm
Theta range for data collection 2.49 to 65.14 deg. Limiting indices -21<=h<=21, -15<=k<=15, -20<=l<=19
Reflections collected / unique 33367 / 7213 [R(int) = 0.0567]
Completeness to theta = 65.14 97.8 % Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.6695 and 0.2190
Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 7213 / 0 / 514
Goodness-of-fit on F^2 1.011 Final R indices [I>2sigma(I)] R1 = 0.0478, wR2 = 0.1117
R indices (all data) R1 = 0.0589, wR2 = 0.1193
Largest diff. peak and hole 2.417 and -3.703 e.Å-3
233
Table 35. Bond Lengths [Å] for (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12)
Atoms Distance Atoms Distance Ga(1)-C(1) 2.019(5) C(13)-C(14) 1.524(8) Ga(1)-Zr(1) 2.7457(9) C(13)-C(16) 1.540(8) Ga(1)-Zr(2) 2.8796(10) C(13)-C(15) 1.535(8) Zr(1)-C(32) 2.467(5) C(17)-C(18) 1.373(7) Zr(1)-C(36) 2.476(5) C(17)-C(22) 1.390(8) Zr(1)-C(33) 2.481(5) C(18)-C(19) 1.396(7) Zr(1)-C(34) 2.481(6) C(19)-C(20) 1.393(7) Zr(1)-C(29) 2.493(6) C(20)-C(21) 1.405(7) Zr(1)-C(28) 2.486(6) C(20)-C(23) 1.527(7) Zr(1)-C(35) 2.495(5) C(21)-C(22) 1.386(7) Zr(1)-C(30) 2.493(5) C(23)-C(25) 1.521(8) Zr(1)-C(31) 2.506(6) C(23)-C(26) 1.537(7) Zr(1)-C(27) 2.512(6) C(23)-C(24) 1.534(7) Zr(1)-Cl(1) 2.6033(13) C(27)-C(28) 1.401(12) Zr(2)-C(37) 2.476(5) C(27)-C(31) 1.397(10) Zr(2)-C(42) 2.480(5) C(28)-C(29) 1.412(10) Zr(2)-C(38) 2.477(5) C(29)-C(30) 1.391(9) Zr(2)-C(46) 2.494(5) C(30)-C(31) 1.403(9) Zr(2)-C(43) 2.493(5) C(32)-C(33) 1.426(8) Zr(2)-C(41) 2.490(5) C(32)-C(36) 1.430(8) Zr(2)-C(44) 2.498(5) C(32)-C(37) 1.458(8) Zr(2)-C(40) 2.500(6) C(33)-C(34) 1.417(8) Zr(2)-C(39) 2.502(5) C(34)-C(35) 1.402(8) Zr(2)-C(45) 2.520(5) C(35)-C(36) 1.410(9) Zr(2)-Cl(1) 2.6141(13) C(37)-C(38) 1.432(8) C(1)-C(6) 1.410(7) C(37)-C(41) 1.440(8) C(1)-C(2) 1.407(7) C(38)-C(39) 1.402(8) C(2)-C(3) 1.395(7) C(39)-C(40) 1.403(9) C(2)-C(7) 1.500(7) C(40)-C(41) 1.410(8) C(3)-C(4) 1.383(7) C(42)-C(43) 1.410(8) C(4)-C(5) 1.382(7) C(42)-C(46) 1.421(9) C(5)-C(6) 1.401(7) C(43)-C(44) 1.410(8) C(6)-C(17) 1.496(7) C(44)-C(45) 1.418(8) C(7)-C(12) 1.385(7) C(45)-C(46) 1.401(8) C(7)-C(8) 1.406(7) C(47)-C(48) 1.374(9) C(8)-C(9) 1.377(7) C(47)-C(52) 1.414(9) C(9)-C(10) 1.402(7) C(47)-C(53) 1.466(10) C(10)-C(11) 1.389(7) C(48)-C(49) 1.424(10) C(10)-C(13) 1.538(7) C(49)-C(50) 1.361(10) C(11)-C(12) 1.391(7) C(50)-C(51) 1.396(9) C(51)-C(52) 1.370(10)
234
Table 36. Bond angles [°] for (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12)
Atoms Angle Atoms Angle C(1)-Ga(1)-Zr(1) 147.58(15) C(30)-Zr(1)-C(31) 32.6(2) C(1)-Ga(1)-Zr(2) 134.53(15) C(32)-Zr(1)-C(27) 155.5(2) Zr(1)-Ga(1)-Zr(2) 77.33(2) C(36)-Zr(1)-C(27) 155.7(2) C(32)-Zr(1)-C(36) 33.63(18) C(33)-Zr(1)-C(27) 122.9(3) C(32)-Zr(1)-C(33) 33.49(19) C(34)-Zr(1)-C(27) 108.9(3) C(36)-Zr(1)-C(33) 54.96(18) C(29)-Zr(1)-C(27) 54.0(2) C(32)-Zr(1)-C(34) 55.4(2) C(28)-Zr(1)-C(27) 32.5(3) C(36)-Zr(1)-C(34) 54.6(2) C(35)-Zr(1)-C(27) 123.3(2) C(33)-Zr(1)-C(34) 33.18(19) C(30)-Zr(1)-C(27) 53.7(2) C(32)-Zr(1)-C(29) 149.2(2) C(31)-Zr(1)-C(27) 32.3(2) C(36)-Zr(1)-C(29) 117.1(2) C(32)-Zr(1)-Cl(1) 82.67(13) C(33)-Zr(1)-C(29) 157.3(2) C(36)-Zr(1)-Cl(1) 76.60(15) C(34)-Zr(1)-C(29) 124.1(2) C(33)-Zr(1)-Cl(1) 115.64(14) C(32)-Zr(1)-C(28) 166.6(2) C(34)-Zr(1)-Cl(1) 131.03(16) C(36)-Zr(1)-C(28) 149.1(2) C(29)-Zr(1)-Cl(1) 78.72(16) C(33)-Zr(1)-C(28) 154.4(3) C(28)-Zr(1)-Cl(1) 86.3(2) C(34)-Zr(1)-C(28) 137.8(2) C(35)-Zr(1)-Cl(1) 104.43(14) C(29)-Zr(1)-C(28) 33.0(2) C(30)-Zr(1)-Cl(1) 105.26(16) C(32)-Zr(1)-C(35) 55.51(19) C(31)-Zr(1)-Cl(1) 132.74(17) C(36)-Zr(1)-C(35) 33.0(2) C(27)-Zr(1)-Cl(1) 118.4(2) C(33)-Zr(1)-C(35) 54.82(18) C(32)-Zr(1)-Ga(1) 88.06(12) C(34)-Zr(1)-C(35) 32.73(19) C(36)-Zr(1)-Ga(1) 121.44(14) C(29)-Zr(1)-C(35) 106.0(2) C(33)-Zr(1)-Ga(1) 79.40(12) C(28)-Zr(1)-C(35) 135.5(2) C(34)-Zr(1)-Ga(1) 105.52(14) C(32)-Zr(1)-C(30) 136.73(18) C(29)-Zr(1)-Ga(1) 118.06(15) C(36)-Zr(1)-C(30) 105.67(19) C(28)-Zr(1)-Ga(1) 85.51(17) C(33)-Zr(1)-C(30) 125.2(2) C(35)-Zr(1)-Ga(1) 134.18(13) C(34)-Zr(1)-C(30) 92.3(2) C(30)-Zr(1)-Ga(1) 131.63(14) C(29)-Zr(1)-C(30) 32.4(2) C(31)-Zr(1)-Ga(1) 104.15(16) C(28)-Zr(1)-C(30) 54.1(2) C(27)-Zr(1)-Ga(1) 77.97(15) C(35)-Zr(1)-C(30) 81.59(19) Cl(1)-Zr(1)-Ga(1) 96.17(4) C(32)-Zr(1)-C(31) 139.2(2) C(37)-Zr(2)-C(42) 137.03(19) C(36)-Zr(1)-C(31) 123.4(2) C(37)-Zr(2)-C(38) 33.60(18) C(33)-Zr(1)-C(31) 109.9(2) C(42)-Zr(2)-C(38) 105.55(19) C(34)-Zr(1)-C(31) 83.8(2) C(37)-Zr(2)-C(46) 140.24(19) C(29)-Zr(1)-C(31) 54.0(2) C(42)-Zr(2)-C(46) 33.2(2) C(28)-Zr(1)-C(31) 54.1(3) C(38)-Zr(2)-C(46) 123.8(2) C(35)-Zr(1)-C(31) 91.2(2) C(37)-Zr(2)-C(43) 148.82(18)
235
Table 36 (con’t). Bond angles [°] for (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12)
Atoms Angle Atoms Angle C(42)-Zr(2)-C(43) 32.94(19) C(37)-Zr(2)-Cl(1) 103.90(15) C(38)-Zr(2)-C(43) 117.31(18) C(38)-Zr(2)-Cl(1) 76.39(14) C(46)-Zr(2)-C(43) 54.7(2) C(46)-Zr(2)-Cl(1) 131.96(15) C(37)-Zr(2)-C(41) 33.71(18) C(43)-Zr(2)-Cl(1) 77.31(14) C(42)-Zr(2)-C(41) 126.6(2) C(41)-Zr(2)-Cl(1) 115.44(14) C(38)-Zr(2)-C(41) 55.15(19) C(44)-Zr(2)-Cl(1) 85.67(14) C(46)-Zr(2)-C(41) 110.9(2) C(40)-Zr(2)-Cl(1) 130.75(15) C(43)-Zr(2)-C(41) 159.21(19) C(39)-Zr(2)-Cl(1) 104.39(14) C(37)-Zr(2)-C(44) 165.33(18) C(45)-Zr(2)-Cl(1) 118.15(14) C(42)-Zr(2)-C(44) 54.47(19) C(37)-Zr(2)-Ga(1) 86.31(13) C(38)-Zr(2)-C(44) 149.15(18) C(42)-Zr(2)-Ga(1) 134.65(14) C(46)-Zr(2)-C(44) 54.3(2) C(38)-Zr(2)-Ga(1) 119.38(14) C(43)-Zr(2)-C(44) 32.83(18) C(46)-Zr(2)-Ga(1) 107.72(14) C(41)-Zr(2)-C(44) 154.61(19) C(43)-Zr(2)-Ga(1) 117.75(13) C(37)-Zr(2)-C(40) 55.21(19) C(41)-Zr(2)-Ga(1) 79.42(14) C(42)-Zr(2)-C(40) 94.0(2) C(44)-Zr(2)-Ga(1) 85.93(13) C(38)-Zr(2)-C(40) 54.6(2) C(40)-Zr(2)-Ga(1) 106.50(14) C(46)-Zr(2)-C(40) 85.0(2) C(39)-Zr(2)-Ga(1) 133.74(14) C(43)-Zr(2)-C(40) 126.4(2) C(45)-Zr(2)-Ga(1) 80.45(12) C(41)-Zr(2)-C(40) 32.81(19) Cl(1)-Zr(2)-Ga(1) 92.76(4) C(44)-Zr(2)-C(40) 139.2(2) Zr(1)-Cl(1)-Zr(2) 84.73(4) C(37)-Zr(2)-C(39) 54.97(19) C(6)-C(1)-C(2) 117.4(4) C(42)-Zr(2)-C(39) 82.71(19) C(6)-C(1)-Ga(1) 124.3(4) C(38)-Zr(2)-C(39) 32.70(19) C(2)-C(1)-Ga(1) 118.3(4) C(46)-Zr(2)-C(39) 92.1(2) C(3)-C(2)-C(1) 121.0(5) C(43)-Zr(2)-C(39) 107.90(19) C(3)-C(2)-C(7) 117.1(4) C(41)-Zr(2)-C(39) 54.37(19) C(1)-C(2)-C(7) 121.9(4) C(44)-Zr(2)-C(39) 137.11(19) C(4)-C(3)-C(2) 120.7(5) C(40)-Zr(2)-C(39) 32.6(2) C(3)-C(4)-C(5) 119.5(5) C(37)-Zr(2)-C(45) 155.93(18) C(4)-C(5)-C(6) 120.5(5) C(42)-Zr(2)-C(45) 54.42(18) C(1)-C(6)-C(5) 120.9(5) C(38)-Zr(2)-C(45) 156.22(19) C(1)-C(6)-C(17) 122.5(4) C(46)-Zr(2)-C(45) 32.46(19) C(5)-C(6)-C(17) 116.6(4) C(43)-Zr(2)-C(45) 54.43(19) C(12)-C(7)-C(8) 117.1(5) C(41)-Zr(2)-C(45) 123.15(19) C(12)-C(7)-C(2) 122.1(5) C(44)-Zr(2)-C(45) 32.84(19) C(8)-C(7)-C(2) 120.6(4) C(40)-Zr(2)-C(45) 109.7(2) C(9)-C(8)-C(7) 120.9(5) C(39)-Zr(2)-C(45) 124.21(19) C(8)-C(9)-C(10) 121.9(5)
236
Table 36 (con’t). Bond angles [°] for (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12)
Atoms Angle Atoms Angle C(11)-C(10)-C(9) 117.2(5) C(31)-C(30)-Zr(1) 74.2(3) C(11)-C(10)-C(13) 122.8(5) C(27)-C(31)-C(30) 107.5(7) C(9)-C(10)-C(13) 119.9(5) C(27)-C(31)-Zr(1) 74.1(4) C(10)-C(11)-C(12) 120.8(5) C(30)-C(31)-Zr(1) 73.2(3) C(7)-C(12)-C(11) 122.1(5) C(33)-C(32)-C(36) 106.4(5) C(14)-C(13)-C(16) 108.4(5) C(33)-C(32)-C(37) 126.9(5) C(14)-C(13)-C(15) 108.4(5) C(36)-C(32)-C(37) 126.6(5) C(16)-C(13)-C(15) 109.7(5) C(33)-C(32)-Zr(1) 73.8(3) C(14)-C(13)-C(10) 112.2(5) C(36)-C(32)-Zr(1) 73.5(3) C(16)-C(13)-C(10) 109.6(4) C(37)-C(32)-Zr(1) 114.6(3) C(15)-C(13)-C(10) 108.6(4) C(32)-C(33)-C(34) 108.2(5) C(18)-C(17)-C(22) 117.8(5) C(32)-C(33)-Zr(1) 72.7(3) C(18)-C(17)-C(6) 120.8(5) C(34)-C(33)-Zr(1) 73.4(3) C(22)-C(17)-C(6) 121.4(5) C(35)-C(34)-C(33) 108.7(5) C(17)-C(18)-C(19) 122.1(5) C(35)-C(34)-Zr(1) 74.2(3) C(20)-C(19)-C(18) 120.8(5) C(33)-C(34)-Zr(1) 73.4(3) C(19)-C(20)-C(21) 116.7(5) C(36)-C(35)-C(34) 107.8(5) C(19)-C(20)-C(23) 122.6(5) C(36)-C(35)-Zr(1) 72.8(3) C(21)-C(20)-C(23) 120.7(5) C(34)-C(35)-Zr(1) 73.1(3) C(22)-C(21)-C(20) 121.8(5) C(35)-C(36)-C(32) 108.9(5) C(17)-C(22)-C(21) 120.8(5) C(35)-C(36)-Zr(1) 74.3(3) C(25)-C(23)-C(20) 112.2(4) C(32)-C(36)-Zr(1) 72.9(3) C(25)-C(23)-C(26) 108.5(4) C(38)-C(37)-C(41) 106.4(5) C(20)-C(23)-C(26) 108.2(4) C(38)-C(37)-C(32) 127.1(5) C(25)-C(23)-C(24) 108.0(4) C(41)-C(37)-C(32) 126.3(5) C(20)-C(23)-C(24) 110.5(4) C(38)-C(37)-Zr(2) 73.2(3) C(26)-C(23)-C(24) 109.4(4) C(41)-C(37)-Zr(2) 73.7(3) C(28)-C(27)-C(31) 108.4(6) C(32)-C(37)-Zr(2) 114.6(3) C(28)-C(27)-Zr(1) 72.7(4) C(39)-C(38)-C(37) 108.4(5) C(31)-C(27)-Zr(1) 73.6(4) C(39)-C(38)-Zr(2) 74.6(3) C(27)-C(28)-C(29) 107.7(6) C(37)-C(38)-Zr(2) 73.2(3) C(27)-C(28)-Zr(1) 74.7(4) C(40)-C(39)-C(38) 108.8(5) C(29)-C(28)-Zr(1) 73.8(3) C(40)-C(39)-Zr(2) 73.6(3) C(30)-C(29)-C(28) 107.6(6) C(38)-C(39)-Zr(2) 72.7(3) C(30)-C(29)-Zr(1) 73.8(3) C(39)-C(40)-C(41) 108.3(5) C(28)-C(29)-Zr(1) 73.3(4) C(39)-C(40)-Zr(2) 73.8(3) C(29)-C(30)-C(31) 108.7(6) C(41)-C(40)-Zr(2) 73.2(3) C(29)-C(30)-Zr(1) 73.8(3) C(40)-C(41)-C(37) 108.0(5)
237
Table 36 (con’t). Bond angles [°] for (C10H8)(ZrCp)2(μ H)(μ Cl)(μ GaR) (12)
Atoms Angle Atoms Angle C(40)-C(41)-Zr(2) 74.0(3) C(46)-C(45)-Zr(2) 72.8(3) C(37)-C(41)-Zr(2) 72.6(3) C(44)-C(45)-Zr(2) 72.7(3) C(43)-C(42)-C(46) 107.9(5) C(45)-C(46)-C(42) 108.2(5) C(43)-C(42)-Zr(2) 74.1(3) C(45)-C(46)-Zr(2) 74.8(3) C(46)-C(42)-Zr(2) 73.9(3) C(42)-C(46)-Zr(2) 72.8(3) C(42)-C(43)-C(44) 107.8(5) C(48)-C(47)-C(52) 119.0(6) C(42)-C(43)-Zr(2) 73.0(3) C(48)-C(47)-C(53) 120.8(6) C(44)-C(43)-Zr(2) 73.8(3) C(52)-C(47)-C(53) 120.1(6) C(43)-C(44)-C(45) 108.3(5) C(47)-C(48)-C(49) 121.1(6) C(43)-C(44)-Zr(2) 73.4(3) C(50)-C(49)-C(48) 119.8(6) C(45)-C(44)-Zr(2) 74.4(3) C(49)-C(50)-C(51) 118.3(7) C(46)-C(45)-C(44) 107.8(5) C(52)-C(51)-C(50) 123.5(7) C(51)-C(52)-C(47) 118.3(7)
238
Structural Data for R TiCp2 (R = 2,6-(4-Me-C6H4)2C6H3-)
Table 37. Crystal data and structural refinement for R TiCp2 (13)
Empirical formula C15H13.50Ti 0.50 Formula weight 217.71 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, C2/c Unit cell dimensions a = 11.1466(7) Å b = 16.4429(11)Å c = 13.0786(8) Å alpha = 90° beta =106.2040(10)° gamma = 90° Volume 2301.9(3) Å3 Z, Calculated density 8, 1.256 Mg/m3 Absorption coefficient 0.386 mm-1 F(000) 916 Crystal size 0.40 x 0.38 x 0.20 mm Theta range for data collection 2.27 to 25.00 deg. Limiting indices -12<=h<=13, -19<=k<=19, -13<=l<=15 Reflections collected / unique 6879 / 2025 [R(int) = 0.0167] Completeness to theta = 25.00 100.00% Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9268 and 0.8609 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 2025 / 0 / 142 Goodness-of-fit on F^2 1.029 Final R indices [I>2sigma(I)] R1 = 0.0373, wR2 = 0.1058 R indices (all data) R1 = 0.0477, wR2 = 0.1157 Largest diff. peak and hole 0.188 and -0.306 e.Å-3
239
Table 38. Bond Lengths [Å] for R TiCp2 (13)
Atoms Distance Atoms Distance Ti(1)-C(1) 2.242(2) C(2)-C(5) 1.485(3) Ti(1)-C(13)#1 2.358(2) C(3)-C(4) 1.373(3) Ti(1)-C(13) 2.358(2) C(4)-C(3)#1 1.373(3) Ti(1)-C(16)#1 2.365(2) C(5)-C(6) 1.389(3) Ti(1)-C(16) 2.365(2) C(5)-C(10) 1.392(3) Ti(1)-C(15) 2.373(2) C(6)-C(7) 1.384(3) Ti(1)-C(15)#1 2.373(2) C(7)-C(8) 1.377(3) Ti(1)-C(14)#1 2.370(2) C(8)-C(9) 1.380(4) Ti(1)-C(14) 2.370(2) C(8)-C(11) 1.521(4) Ti(1)-C(12)#1 2.369(2) C(9)-C(10) 1.373(3) Ti(1)-C(12) 2.369(2) C(12)-C(16) 1.362(4) C(1)-C(2)#1 1.421(2) C(12)-C(13) 1.338(4) C(1)-C(2) 1.421(2) C(13)-C(14) 1.370(4) C(2)-C(3) 1.402(3) C(14)-C(15) 1.401(4) C(15)-C(16) 1.390(4)
240
Table 39. Bond angles [°] for R TiCp2 (13)
Atoms Distance Atoms Distance C(1)-Ti(1)-C(13)#1 111.31(8) C(13)-Ti(1)-C(12)#1 106.40(12) C(1)-Ti(1)-C(13) 111.31(8) C(16)#1-Ti(1)-C(12)#1 33.45(9) C(13)#1-Ti(1)-C(13) 137.38(16) C(16)-Ti(1)-C(12)#1 86.30(11) C(1)-Ti(1)-C(16)#1 125.87(8) C(15)-Ti(1)-C(12)#1 119.67(11) C(13)#1-Ti(1)-C(16)#1 55.75(9) C(15)#1-Ti(1)-C(12)#1 55.76(9) C(13)-Ti(1)-C(16)#1 97.87(11) C(14)#1-Ti(1)-C(12)#1 55.38(10) C(1)-Ti(1)-C(16) 125.87(8) C(14)-Ti(1)-C(12)#1 135.19(10) C(13)#1-Ti(1)-C(16) 97.87(11) C(1)-Ti(1)-C(12) 140.09(7) C(13)-Ti(1)-C(16) 55.75(9) C(13)#1-Ti(1)-C(12) 106.40(12) C(16)#1-Ti(1)-C(16) 108.26(17) C(13)-Ti(1)-C(12) 32.87(10) C(1)-Ti(1)-C(15) 92.53(8) C(16)#1-Ti(1)-C(12) 86.30(11) C(13)#1-Ti(1)-C(15) 121.57(12) C(16)-Ti(1)-C(12) 33.45(9) C(13)-Ti(1)-C(15) 56.24(10) C(15)-Ti(1)-C(12) 55.76(9) C(16)#1-Ti(1)-C(15) 140.91(12) C(15)#1-Ti(1)-C(12) 119.67(11) C(16)-Ti(1)-C(15) 34.12(10) C(14)#1-Ti(1)-C(12) 135.19(10) C(1)-Ti(1)-C(15)#1 92.53(8) C(14)-Ti(1)-C(12) 55.38(10) C(13)#1-Ti(1)-C(15)#1 56.25(10) C(12)#1-Ti(1)-C(12) 79.82(15) C(13)-Ti(1)-C(15)#1 121.57(12) C(2)#1-C(1)-C(2) 114.8(2) C(16)#1-Ti(1)-C(15)#1 34.12(10) C(2)#1-C(1)-Ti(1) 122.59(11) C(16)-Ti(1)-C(15)#1 140.91(12) C(2)-C(1)-Ti(1) 122.59(11) C(15)-Ti(1)-C(15)#1 174.94(16) C(3)-C(2)-C(1) 122.09(19) C(1)-Ti(1)-C(14)#1 84.71(7) C(3)-C(2)-C(5) 116.74(17) C(13)#1-Ti(1)-C(14)#1 33.68(10) C(1)-C(2)-C(5) 121.16(17) C(13)-Ti(1)-C(14)#1 154.04(11) C(4)-C(3)-C(2) 120.8(2) C(16)#1-Ti(1)-C(14)#1 56.50(9) C(3)-C(4)-C(3)#1 119.3(3) C(16)-Ti(1)-C(14)#1 131.30(11) C(6)-C(5)-C(10) 116.36(19) C(15)-Ti(1)-C(14)#1 146.47(10) C(6)-C(5)-C(2) 121.59(17) C(15)#1-Ti(1)-C(14)#1 34.36(11) C(10)-C(5)-C(2) 122.05(17) C(1)-Ti(1)-C(14) 84.71(7) C(7)-C(6)-C(5) 121.74(19) C(13)#1-Ti(1)-C(14) 154.04(11) C(8)-C(7)-C(6) 121.3(2) C(13)-Ti(1)-C(14) 33.68(10) C(7)-C(8)-C(9) 117.1(2) C(16)#1-Ti(1)-C(14) 131.30(11) C(7)-C(8)-C(11) 120.8(2) C(16)-Ti(1)-C(14) 56.50(9) C(9)-C(8)-C(11) 122.1(2) C(15)-Ti(1)-C(14) 34.36(11) C(10)-C(9)-C(8) 122.0(2) C(15)#1-Ti(1)-C(14) 146.47(10) C(9)-C(10)-C(5) 121.4(2) C(14)#1-Ti(1)-C(14) 169.43(14) C(16)-C(12)-C(13) 109.8(3) C(1)-Ti(1)-C(12)#1 140.09(7) C(16)-C(12)-Ti(1) 73.11(14) C(13)#1-Ti(1)-C(12)#1 32.87(10) C(13)-C(12)-Ti(1) 73.12(14)
241
Table 39 (con’t). Bond angles [°] for R TiCp2 (13)
Atoms Distance Atoms Distance C(14)-C(13)-C(12) 108.9(3) C(16)-C(15)-C(14) 106.8(2) C(14)-C(13)-Ti(1) 73.64(15) C(16)-C(15)-Ti(1) 72.64(15) C(12)-C(13)-Ti(1) 74.01(15) C(14)-C(15)-Ti(1) 72.73(14) C(13)-C(14)-C(15) 107.2(2) C(12)-C(16)-C(15) 107.3(2) C(13)-C(14)-Ti(1) 72.68(15) C(12)-C(16)-Ti(1) 73.44(14) C(15)-C(14)-Ti(1) 72.91(15) C(15)-C(16)-Ti(1) 73.25(14)
242
Structural Data for (R)(Cl)ZrCp2 (14) (R = 2,6-(4-t-BuC6H4)2C6H3-)
Table 40. Crystal data and structural refinement for (R)(Cl)ZrCp2 (14)
Empirical formula C79H86Cl2Zr2
Formula weight 1288.82
Temperature 273(2) K
Wavelength 0.71073 Å
Crystal system, space group Monoclinic, P2(1)/n
Unit cell dimensions a = 18.9577(10) Å
b = 9.2362(5) Å
c = 19.2877(10) Å
= 90°
= 96.9220(10)° .
= 90°
Volume 3352.6(3) Å3
Z, Calculated density 2, 1.277 Mg/m3
Absorption coefficient 0.433 mm-1
F(000) 1348
Crystal size 0.33 x 0.23 x 0.09 mm
Theta range for data collection 2.45 to 25.00 deg.
Limiting indices -22<=h<=22, -10<=k<=10, -22<=l<=22
Reflections collected / unique 21486 / 5880 [R(int) = 0.0478]
Completeness to theta = 25.00 99.60%
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.9621 and 0.8703
Refinement method Full-matrix least-squares on F^2
Data / restraints / parameters 5880 / 13 / 380
Goodness-of-fit on F^2 1.054
Final R indices [I>2sigma(I)] R1 = 0.0431, wR2 = 0.0999
R indices (all data) R1 = 0.0807, wR2 = 0.1190
Largest diff. peak and hole 0.561 and -0.434 e.Å-3
243
Table 41. Bond Lengths [Å] for (R)(Cl)ZrCp2 (14) Atoms Distance Atoms Distance Zr(1)-C(1) 2.380(4) C(13)-C(14) 1.534(6) Zr(1)-Cl(1) 2.4612(12) C(13)-C(16) 1.529(6) Zr(1)-C(33) 2.488(4) C(13)-C(15) 1.529(6) Zr(1)-C(27) 2.491(4) C(17)-C(18) 1.379(5) Zr(1)-C(28) 2.497(4) C(17)-C(22) 1.385(6) Zr(1)-C(34) 2.505(4) C(18)-C(19) 1.394(6) Zr(1)-C(32) 2.500(4) C(19)-C(20) 1.382(6) Zr(1)-C(36) 2.506(4) C(20)-C(21) 1.383(5) Zr(1)-C(35) 2.513(4) C(20)-C(23) 1.526(5) Zr(1)-C(31) 2.515(4) C(21)-C(22) 1.382(5) Zr(1)-C(30) 2.523(4) C(23)-C(25) 1.498(7) Zr(1)-C(29) 2.534(4) C(23)-C(26) 1.520(7) C(1)-C(2) 1.411(5) C(23)-C(24) 1.533(7) C(1)-C(6) 1.426(5) C(27)-C(28) 1.386(6) C(2)-C(3) 1.390(5) C(27)-C(31) 1.397(6) C(2)-C(7) 1.486(5) C(28)-C(29) 1.364(6) C(3)-C(4) 1.368(6) C(29)-C(30) 1.406(6) C(4)-C(5) 1.372(6) C(30)-C(31) 1.399(6) C(5)-C(6) 1.391(5) C(32)-C(36) 1.391(7) C(6)-C(17) 1.508(5) C(32)-C(33) 1.411(6) C(7)-C(12) 1.388(5) C(33)-C(34) 1.402(6) C(7)-C(8) 1.390(5) C(34)-C(35) 1.380(6) C(8)-C(9) 1.370(5) C(35)-C(36) 1.399(7) C(9)-C(10) 1.392(5) C(37)-C(38) 1.136(14) C(10)-C(11) 1.394(5) C(38)-C(40)#1 1.480(16) C(10)-C(13) 1.519(6) C(38)-C(39) 1.395(12) C(11)-C(12) 1.370(5) C(39)-C(40) 1.329(17) C(40)-C(38)#1 1.480(16)
244
Table 42. Bond Angles [°] for (R)(Cl)ZrCp2 (14) Atoms Angle Atoms Angle C(1)-Zr(1)-Cl(1) 118.79(9) C(27)-Zr(1)-C(31) 32.39(13) C(1)-Zr(1)-C(33) 91.79(14) C(28)-Zr(1)-C(31) 53.26(15) Cl(1)-Zr(1)-C(33) 129.82(12) C(34)-Zr(1)-C(31) 116.91(16) C(1)-Zr(1)-C(27) 94.23(15) C(32)-Zr(1)-C(31) 128.19(18) Cl(1)-Zr(1)-C(27) 127.78(12) C(36)-Zr(1)-C(31) 160.22(19) C(33)-Zr(1)-C(27) 83.57(16) C(35)-Zr(1)-C(31) 146.77(17) C(1)-Zr(1)-C(28) 124.49(15) C(1)-Zr(1)-C(30) 88.04(14) Cl(1)-Zr(1)-C(28) 98.60(13) Cl(1)-Zr(1)-C(30) 86.33(13) C(33)-Zr(1)-C(28) 93.74(16) C(33)-Zr(1)-C(30) 136.85(16) C(27)-Zr(1)-C(28) 32.28(15) C(27)-Zr(1)-C(30) 53.46(15) C(1)-Zr(1)-C(34) 124.28(15) C(28)-Zr(1)-C(30) 53.00(15) Cl(1)-Zr(1)-C(34) 104.15(13) C(34)-Zr(1)-C(30) 130.57(15) C(33)-Zr(1)-C(34) 32.61(15) C(32)-Zr(1)-C(30) 159.78(19) C(27)-Zr(1)-C(34) 84.90(16) C(36)-Zr(1)-C(30) 167.55(19) C(28)-Zr(1)-C(34) 77.60(16) C(35)-Zr(1)-C(30) 143.13(18) C(1)-Zr(1)-C(32) 76.93(15) C(31)-Zr(1)-C(30) 32.23(14) Cl(1)-Zr(1)-C(32) 112.67(14) C(1)-Zr(1)-C(29) 120.09(14) C(33)-Zr(1)-C(32) 32.87(15) Cl(1)-Zr(1)-C(29) 75.03(12) C(27)-Zr(1)-C(32) 113.57(18) C(33)-Zr(1)-C(29) 124.90(16) C(28)-Zr(1)-C(32) 126.32(16) C(27)-Zr(1)-C(29) 53.03(15) C(34)-Zr(1)-C(32) 53.65(16) C(28)-Zr(1)-C(29) 31.45(14) C(1)-Zr(1)-C(36) 98.11(17) C(34)-Zr(1)-C(29) 103.33(16) Cl(1)-Zr(1)-C(36) 81.22(15) C(32)-Zr(1)-C(29) 156.44(16) C(33)-Zr(1)-C(36) 54.17(17) C(36)-Zr(1)-C(29) 141.23(19) C(27)-Zr(1)-C(36) 136.07(16) C(35)-Zr(1)-C(29) 110.95(18) C(28)-Zr(1)-C(36) 128.72(16) C(31)-Zr(1)-C(29) 53.21(15) C(34)-Zr(1)-C(36) 53.56(16) C(30)-Zr(1)-C(29) 32.28(14) C(32)-Zr(1)-C(36) 32.27(16) C(2)-C(1)-C(6) 114.7(3) C(1)-Zr(1)-C(35) 128.83(16) C(2)-C(1)-Zr(1) 114.9(3) Cl(1)-Zr(1)-C(35) 76.51(13) C(6)-C(1)-Zr(1) 129.4(2) C(33)-Zr(1)-C(35) 53.69(17) C(3)-C(2)-C(1) 122.8(4) C(27)-Zr(1)-C(35) 114.48(17) C(3)-C(2)-C(7) 115.9(3) C(28)-Zr(1)-C(35) 97.21(17) C(1)-C(2)-C(7) 121.3(3) C(34)-Zr(1)-C(35) 31.92(15) C(4)-C(3)-C(2) 120.7(4) C(32)-Zr(1)-C(35) 53.33(17) C(3)-C(4)-C(5) 118.4(4) C(36)-Zr(1)-C(35) 32.37(16) C(4)-C(5)-C(6) 122.3(4) C(1)-Zr(1)-C(31) 72.53(13) C(5)-C(6)-C(1) 120.9(4) Cl(1)-Zr(1)-C(31) 118.55(12) C(5)-C(6)-C(17) 113.8(4) C(33)-Zr(1)-C(31) 107.75(17) C(1)-C(6)-C(17) 125.3(3)
245
Table 42 (con’t.). Bond Angles [°] for (R)(Cl)ZrCp2 (14) Atoms Angle Atoms Angle C(12)-C(7)-C(8) 116.6(4) C(28)-C(27)-Zr(1) 74.1(3) C(12)-C(7)-C(2) 123.4(3) C(31)-C(27)-Zr(1) 74.8(2) C(8)-C(7)-C(2) 119.8(3) C(29)-C(28)-C(27) 109.3(4) C(9)-C(8)-C(7) 121.4(4) C(29)-C(28)-Zr(1) 75.8(2) C(8)-C(9)-C(10) 122.1(4) C(27)-C(28)-Zr(1) 73.6(2) C(11)-C(10)-C(9) 116.3(4) C(28)-C(29)-C(30) 107.9(4) C(11)-C(10)-C(13) 123.6(4) C(28)-C(29)-Zr(1) 72.8(2) C(9)-C(10)-C(13) 120.0(4) C(30)-C(29)-Zr(1) 73.5(2) C(12)-C(11)-C(10) 121.5(4) C(31)-C(30)-C(29) 107.5(4) C(11)-C(12)-C(7) 122.1(4) C(31)-C(30)-Zr(1) 73.6(2) C(10)-C(13)-C(14) 112.7(4) C(29)-C(30)-Zr(1) 74.3(2) C(10)-C(13)-C(16) 108.9(3) C(27)-C(31)-C(30) 107.6(4) C(14)-C(13)-C(16) 106.8(4) C(27)-C(31)-Zr(1) 72.8(2) C(10)-C(13)-C(15) 109.9(4) C(30)-C(31)-Zr(1) 74.2(2) C(14)-C(13)-C(15) 108.2(4) C(36)-C(32)-C(33) 108.5(5) C(16)-C(13)-C(15) 110.2(4) C(36)-C(32)-Zr(1) 74.1(3) C(18)-C(17)-C(22) 116.8(4) C(33)-C(32)-Zr(1) 73.1(2) C(18)-C(17)-C(6) 120.8(4) C(34)-C(33)-C(32) 106.8(5) C(22)-C(17)-C(6) 121.8(3) C(34)-C(33)-Zr(1) 74.4(2) C(17)-C(18)-C(19) 121.2(4) C(32)-C(33)-Zr(1) 74.0(2) C(20)-C(19)-C(18) 122.3(4) C(35)-C(34)-C(33) 108.6(5) C(19)-C(20)-C(21) 115.6(4) C(35)-C(34)-Zr(1) 74.4(2) C(19)-C(20)-C(23) 123.2(4) C(33)-C(34)-Zr(1) 73.0(2) C(21)-C(20)-C(23) 121.2(4) C(34)-C(35)-C(36) 108.7(5) C(20)-C(21)-C(22) 122.7(4) C(34)-C(35)-Zr(1) 73.7(3) C(17)-C(22)-C(21) 121.2(4) C(36)-C(35)-Zr(1) 73.6(2) C(25)-C(23)-C(26) 111.2(5) C(32)-C(36)-C(35) 107.5(5) C(25)-C(23)-C(20) 109.4(4) C(32)-C(36)-Zr(1) 73.6(2) C(26)-C(23)-C(20) 109.7(4) C(35)-C(36)-Zr(1) 74.1(3) C(25)-C(23)-C(24) 107.4(5) C(40)#1-C(38)-C(37) 97.6(13) C(26)-C(23)-C(24) 107.7(5) C(40)#1-C(38)-C(39) 113.0(9) C(20)-C(23)-C(24) 111.4(4) C(37)-C(38)-C(39) 149.4(16) C(28)-C(27)-C(31) 107.7(4) C(38)-C(39)-C(40) 137.1(15) C(38)#1-C(40)-C(39) 109.8(17)
246
Structural Data for 2,2’-Z-dibromostilbene (15) Table 43. Crystal data and structural refinement for 2,2’-Z-dibromostilbene (15) Empirical formula C14H10Br2 Formula weight 338.04 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, C2/c Unit cell dimensions a = 16.133(4) Å b = 14.983(4) Å c = 11.328(3) Å = 90°
= 113.031(4)°
= 90°
Volume 2519.9(11) Å3 Z, Calculated density 8, 1.782 Mg/m3 Absorption coefficient 6.402 mm-1 F(000) 1312 Crystal size 0.50 x 0.28 x 0.10 mm Theta range for data collection 1.93 to 25.00 deg. Limiting indices -19<=h<=18, -17<=k<=17, -13<=l<=13 Reflections collected / unique 8088 / 2220 [R(int) = 0.0231] Completeness to theta = 25.00 100.00% Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.5669 and 0.1420 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 2220 / 0 / 145 Goodness-of-fit on F^2 1.047 Final R indices [I>2sigma(I)] R1 = 0.0427, wR2 = 0.0917 R indices (all data) 0.752 and -0.768 e.Å-3
247
Table 44. Bond Lengths [Å] for 2,2’-Z-dibromostilbene (15) Atoms Distance Atoms Distance Br(1)-C(1) 1.903(4) C(6)-C(7) 1.464(6) Br(2)-C(14) 1.898(5) C(7)-C(8) 1.328(6) C(1)-C(2) 1.382(7) C(8)-C(9) 1.479(6) C(1)-C(6) 1.390(6) C(9)-C(14) 1.379(6) C(2)-C(3) 1.373(7) C(9)-C(10) 1.388(7) C(3)-C(4) 1.373(7) C(10)-C(11) 1.379(7) C(4)-C(5) 1.371(7) C(11)-C(12) 1.361(8) C(5)-C(6) 1.396(6) C(12)-C(13) 1.364(8) C(13)-C(14) 1.374(7)
Table 45. Bond angles [°] for 2,2’-Z-dibromostilbene (15) Atoms Angle Atoms Angle C(2)-C(1)-C(6) 122.6(4) C(7)-C(8)-C(9) 126.8(5) C(2)-C(1)-Br(1) 117.9(4) C(14)-C(9)-C(10) 116.7(4) C(6)-C(1)-Br(1) 119.6(4) C(14)-C(9)-C(8) 121.9(4) C(3)-C(2)-C(1) 119.4(5) C(10)-C(9)-C(8) 121.3(4) C(4)-C(3)-C(2) 119.8(5) C(11)-C(10)-C(9) 120.9(5) C(3)-C(4)-C(5) 120.3(5) C(12)-C(11)-C(10) 120.7(5) C(4)-C(5)-C(6) 121.9(4) C(13)-C(12)-C(11) 119.7(5) C(1)-C(6)-C(5) 116.0(4) C(12)-C(13)-C(14) 119.5(5) C(1)-C(6)-C(7) 122.2(4) C(9)-C(14)-C(13) 122.5(5) C(5)-C(6)-C(7) 121.6(4) C(9)-C(14)-Br(2) 118.8(4) C(8)-C(7)-C(6) 128.3(4) C(13)-C(14)-Br(2) 118.7(4)
248
Structural Data for 2,2’-dilithio-Z-stilbene(TMEDA)2 (16) Table 46. Crystal data and structural refinement for 2,2’-dilithio-Z-stilbene(TMEDA)2 (16) Empirical formula C26H42Li2N4
Formula weight 424.52 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/m Unit cell dimensions a = 9.628(3) Å b = 12.277(3) Å c = 12.009(3) Å = 90° = 92.147(4)°
= 90° Volume 1418.5(7) Å3
Z, Calculated density 2, 0.994 Mg/m3
Absorption coefficient 0.058 mm-1
F(000) 464 Crystal size 0.22 x 0.22 x 0.07 mm Theta range for data collection 2.12 to 25.00 deg. Limiting indices -11<=h<=11, -13<=k<=14, -14<=l<=14 Reflections collected / unique 9491 / 2634 [R(int) = 0.0317] Completeness to theta = 25.00 100.00%
Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9960 and 0.9875 Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 2634 / 84 / 198 Goodness-of-fit on F^2 1.011 Final R indices [I>2sigma(I)] R1 = 0.0561, wR2 = 0.1581 R indices (all data) R1 = 0.1280, wR2 = 0.2043 Largest diff. peak and hole 0.107 and -0.107 e.Å-3
249
Table 47. Bond Lengths [Å] for 2,2’-dilithio-Z-stilbene(TMEDA)2 (16) Atoms Distance Atoms Distance Li(1)-C(1)#1 2.158(4) N(3)-C(12')#1 1.507(19) Li(1)-C(1) 2.158(4) N(3)-C(12') 1.507(19) Li(1)-N(2) 2.155(6) N(3)-C(15)#1 1.456(4) Li(1)-N(1) 2.194(7) N(3)-C(15) 1.456(4) Li(1)-Li(2) 2.527(8) N(3)-C(12) 1.473(13) Li(2)-C(1)#1 2.157(4) N(3)-C(12)#1 1.473(13) Li(2)-C(1) 2.157(4) N(4)-C(14)#1 1.428(4) Li(2)-N(3) 2.187(7) N(4)-C(14) 1.428(5) Li(2)-N(4) 2.247(6) N(4)-C(13)#1 1.47(2) Li(2)-C(12')#1 2.84(3) N(4)-C(13) 1.47(2) Li(2)-C(12') 2.84(3) N(4)-C(13')#1 1.527(19) N(1)-C(10)#1 1.452(4) N(4)-C(13') 1.527(19) N(1)-C(10) 1.452(4) C(1)-C(2) 1.405(3) N(1)-C(8) 1.52(2) C(1)-C(6) 1.420(3) N(1)-C(8)#1 1.52(2) C(2)-C(3) 1.379(4) N(1)-C(8')#1 1.519(18) C(3)-C(4) 1.362(5) N(1)-C(8') 1.519(18) C(4)-C(5) 1.345(4) N(2)-C(11)#1 1.453(4) C(5)-C(6) 1.394(3) N(2)-C(11) 1.453(4) C(6)-C(7) 1.463(3) N(2)-C(9)#1 1.507(18) C(7)-C(7)#1 1.340(5) N(2)-C(9) 1.507(18) C(8)-C(9) 1.443(16) N(2)-C(9') 1.518(19) C(8')-C(9') 1.468(18) N(2)-C(9')#1 1.518(19) C(12)-C(13) 1.480(16) C(12')-C(13') 1.479(19)
250
Table 48. Bond angles [°] for 2,2’-dilithio-Z-stilbene(TMEDA)2 (16) Atoms Angle Atoms Angle C(1)#1-Li(1)-C(1) 100.8(3) C(10)-N(1)-C(8')#1 108.4(6) C(1)#1-Li(1)-N(2) 119.93(17) C(8)-N(1)-C(8')#1 26.8(14) C(1)-Li(1)-N(2) 119.93(17) C(8)#1-N(1)-C(8')#1 26.8(14) C(1)#1-Li(1)-N(1) 116.51(18) C(10)#1-N(1)-C(8') 108.4(6) C(1)-Li(1)-N(1) 116.51(18) C(10)-N(1)-C(8') 108.4(6) N(2)-Li(1)-N(1) 84.0(2) C(8)-N(1)-C(8') 26.8(14) C(1)#1-Li(1)-Li(2) 54.13(14) C(8)#1-N(1)-C(8') 26.8(14) C(1)-Li(1)-Li(2) 54.13(14) C(8')#1-N(1)-C(8') 0.0(2) N(2)-Li(1)-Li(2) 118.3(3) C(10)#1-N(1)-Li(1) 112.5(2) N(1)-Li(1)-Li(2) 157.7(3) C(10)-N(1)-Li(1) 112.5(2) C(1)#1-Li(2)-C(1) 100.9(3) C(8)-N(1)-Li(1) 97.5(10) C(1)#1-Li(2)-N(3) 112.98(19) C(8)#1-N(1)-Li(1) 97.5(10) C(1)-Li(2)-N(3) 112.98(19) C(8')#1-N(1)-Li(1) 105.2(10) C(1)#1-Li(2)-N(4) 122.81(17) C(8')-N(1)-Li(1) 105.2(10) C(1)-Li(2)-N(4) 122.81(17) C(11)#1-N(2)-C(11) 109.2(4) N(3)-Li(2)-N(4) 83.9(2) C(11)#1-N(2)-C(9)#1 109.3(4) C(1)#1-Li(2)-Li(1) 54.17(14) C(11)-N(2)-C(9)#1 109.3(4) C(1)-Li(2)-Li(1) 54.17(14) C(11)#1-N(2)-C(9) 109.3(4) N(3)-Li(2)-Li(1) 151.0(3) C(11)-N(2)-C(9) 109.3(4) N(4)-Li(2)-Li(1) 125.0(3) C(9)#1-N(2)-C(9) 0.0(14) C(1)#1-Li(2)-C(12')#1 112.0(10) C(11)#1-N(2)-C(9') 135.1(14) C(1)-Li(2)-C(12')#1 139.1(10) C(11)-N(2)-C(9') 88.1(12) N(3)-Li(2)-C(12')#1 31.7(6) C(9)#1-N(2)-C(9') 27.6(14) N(4)-Li(2)-C(12')#1 56.6(5) C(9)-N(2)-C(9') 27.6(14) Li(1)-Li(2)-C(12')#1 165.7(10) C(11)#1-N(2)-C(9')#1 88.1(12) C(1)#1-Li(2)-C(12') 139.1(10) C(11)-N(2)-C(9')#1 135.1(15) C(1)-Li(2)-C(12') 112.0(10) C(9)#1-N(2)-C(9')#1 27.6(14) N(3)-Li(2)-C(12') 31.7(6) C(9)-N(2)-C(9')#1 27.6(14) N(4)-Li(2)-C(12') 56.6(5) C(9')-N(2)-C(9')#1 54(3) Li(1)-Li(2)-C(12') 165.7(10) C(11)#1-N(2)-Li(1) 110.9(2) C(12')#1-Li(2)-C(12') 29(2) C(11)-N(2)-Li(1) 110.9(2) C(10)#1-N(1)-C(10) 109.6(4) C(9)#1-N(2)-Li(1) 107.0(7) C(11)#1-N(2)-C(9) 133.7(14) C(9)-N(2)-Li(1) 107.0(7) C(10)-N(1)-C(8) 88.6(11) C(9')-N(2)-Li(1) 99.8(12) C(10)#1-N(1)-C(8)#1 88.6(11) C(9')#1-N(2)-Li(1) 99.8(12) C(10)-N(1)-C(8)#1 133.7(14) C(12')#1-N(3)-C(12') 56(4) C(8)-N(1)-C(8)#1 52(3) C(12')#1-N(3)-C(15)#1 87.3(14) C(10)#1-N(1)-C(8')#1 108.4(6) C(12')-N(3)-C(15)#1 136(2)
251
Table 48 (con’t.). Bond angles [°] for 2,2’-dilithio-Z-stilbene(TMEDA)2 (16) Atoms Angle Atoms Angle C(12')#1-N(3)-C(15) 136(2) C(13)-N(4)-C(13') 25.2(17) C(12')-N(3)-C(15) 87.3(14) C(13')#1-N(4)-C(13') 0.0(17) C(15)#1-N(3)-C(15) 109.6(5) C(14)#1-N(4)-Li(2) 113.1(3) C(12')#1-N(3)-C(12) 28(2) C(14)-N(4)-Li(2) 113.1(3) C(12')-N(3)-C(12) 28(2) C(13)#1-N(4)-Li(2) 97.5(10) C(15)#1-N(3)-C(12) 109.0(4) C(13)-N(4)-Li(2) 97.5(10) C(15)-N(3)-C(12) 109.0(4) C(13')#1-N(4)-Li(2) 103.7(13) C(12')#1-N(3)-C(12)#1 28(2) C(13')-N(4)-Li(2) 103.7(13) C(12')-N(3)-C(12)#1 28(2) C(2)-C(1)-C(6) 113.5(2) C(15)#1-N(3)-C(12)#1 109.0(4) C(2)-C(1)-Li(2) 119.0(2) C(15)-N(3)-C(12)#1 109.0(4) C(6)-C(1)-Li(2) 110.9(2) C(12)-N(3)-C(12)#1 0.0(13) C(2)-C(1)-Li(1) 128.8(2) C(12')#1-N(3)-Li(2) 98.6(16) C(6)-C(1)-Li(1) 106.0(2) C(12')-N(3)-Li(2) 98.6(16) Li(2)-C(1)-Li(1) 71.69(18) C(15)#1-N(3)-Li(2) 111.4(2) C(3)-C(2)-C(1) 124.5(3) C(15)-N(3)-Li(2) 111.4(2) C(4)-C(3)-C(2) 119.3(3) C(12)-N(3)-Li(2) 106.3(7) C(5)-C(4)-C(3) 119.5(3) C(12)#1-N(3)-Li(2) 106.3(7) C(4)-C(5)-C(6) 122.2(3) C(14)#1-N(4)-C(14) 110.4(6) C(5)-C(6)-C(1) 120.9(2) C(14)#1-N(4)-C(13)#1 88.8(12) C(5)-C(6)-C(7) 114.2(2) C(14)-N(4)-C(13)#1 131.6(16) C(1)-C(6)-C(7) 124.9(2) C(14)#1-N(4)-C(13) 131.6(16) C(7)#1-C(7)-C(6) 139.70(12) C(14)-N(4)-C(13) 88.8(12) C(9)-C(8)-N(1) 114(2) C(13)#1-N(4)-C(13) 49(3) C(8)-C(9)-N(2) 109.1(16) C(14)#1-N(4)-C(13')#1 108.0(8) C(9')-C(8')-N(1) 110(2) C(14)-N(4)-C(13')#1 108.0(7) C(8')-C(9')-N(2) 111(2) C(13)#1-N(4)-C(13')#1 25.2(17) C(13)-C(12)-N(3) 111.7(15) C(13)-N(4)-C(13')#1 25.2(17) C(12)-C(13)-N(4) 115.9(19) C(14)#1-N(4)-C(13') 108.0(8) N(3)-C(12')-C(13') 112(3) C(14)-N(4)-C(13') 108.0(7) N(3)-C(12')-Li(2) 49.7(10) C(13)#1-N(4)-C(13') 25.2(17) C(13')-C(12')-Li(2) 81.6(18) C(12')-C(13')-N(4) 110(2)
252
Structural Data for [(spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)] (17).
Table 49. Crystal data and structural refinement for [(spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)] (17). Empirical formula C32H30GaLiO Formula weight 507.22 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/n Unit cell dimensions a = 11.141(2) Å b = 29.107(5) Å c = 16.640(3) Å = 90°
= 90.551(3)°
= 90°
Volume 5396.0(17) Å3 Z, Calculated density 8, 1.249 Mg/m3 Absorption coefficient 1.041 mm-1 F(000) 2112 Crystal size 0.20 x 0.16 x 0.08 mm Theta range for data collection 1.86 to 25.00 deg. Limiting indices -13<=h<=13, -34<=k<=34, -19<=l<=19 Reflections collected / unique 57574 / 9498 [R(int) = 0.1282] Completeness to theta = 25.00 100.00% Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9213 and 0.8188 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 9498 / 160 / 705 Goodness-of-fit on F^2 1.037 Final R indices [I>2sigma(I)] R1 = 0.0461, wR2 = 0.0693 R indices (all data) R1 = 0.1216, wR2 = 0.0893 Largest diff. peak and hole 0.222 and -0.219 eÅ-3
253
Table 50. Bond Lengths [Å] for [(spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)] (17). Atoms Distance Atoms Distance Ga(1)-C(1) 1.972(4) C(16)-C(17) 1.388(5) Ga(1)-C(15) 1.987(4) C(17)-C(18) 1.370(6) Ga(1)-C(10) 2.022(4) C(18)-C(19) 1.350(6) Ga(1)-C(24) 2.030(4) C(19)-C(20) 1.410(6) Ga(1)-Li(1) 2.722(9) C(20)-C(21) 1.472(6) Ga(2)-C(47) 1.968(4) C(21)-C(22) 1.351(6) Ga(2)-C(33) 1.968(4) C(22)-C(23) 1.464(6) Ga(2)-C(56) 2.013(4) C(23)-C(24) 1.405(5) Ga(2)-C(42) 2.020(4) C(23)-C(28) 1.411(6) Ga(2)-Li(2) 2.775(8) C(24)-C(25) 1.395(5) Li(1)-O(1) 1.849(10) C(25)-C(26) 1.388(6) Li(1)-C(24) 2.294(9) C(26)-C(27) 1.375(6) Li(1)-C(10) 2.368(10) C(27)-C(28) 1.360(6) Li(1)-C(9) 2.488(9) O(1)-C(30') 1.305(17) Li(1)-C(8) 2.586(11) O(1)-C(31') 1.41(2) Li(1)-C(23) 2.638(10) O(1)-C(31) 1.588(18) Li(2)-O(2) 1.815(9) O(1)-C(30) 1.590(17) Li(2)-C(56) 2.305(9) C(29)-C(30) 1.30(3) Li(2)-C(42) 2.305(9) C(31)-C(32) 1.58(2) Li(2)-C(55) 2.568(9) C(29')-C(30') 1.47(3) Li(2)-C(41) 2.543(9) C(31')-C(32') 1.38(4) C(1)-C(6) 1.412(5) C(33)-C(38) 1.400(6) C(1)-C(2) 1.400(5) C(33)-C(34) 1.400(6) C(2)-C(3) 1.382(5) C(34)-C(35) 1.395(7) C(3)-C(4) 1.367(5) C(35)-C(36) 1.367(8) C(4)-C(5) 1.364(5) C(36)-C(37) 1.347(8) C(5)-C(6) 1.401(5) C(37)-C(38) 1.415(7) C(6)-C(7) 1.469(5) C(38)-C(39) 1.470(7) C(7)-C(8) 1.339(5) C(39)-C(40) 1.351(7) C(8)-C(9) 1.467(5) C(40)-C(41) 1.446(7) C(9)-C(10) 1.405(5) C(41)-C(42) 1.392(6) C(9)-C(14) 1.414(5) C(41)-C(46) 1.422(7) C(10)-C(11) 1.401(5) C(42)-C(43) 1.395(5) C(11)-C(12) 1.379(5) C(43)-C(44) 1.374(6) C(12)-C(13) 1.374(6) C(44)-C(45) 1.363(8) C(13)-C(14) 1.357(6) C(45)-C(46) 1.352(8) C(15)-C(20) 1.403(5) C(47)-C(48) 1.387(5) C(15)-C(16) 1.392(5) C(47)-C(52) 1.409(5)
254
Table 50 (Cont.). Bond Lengths [Å] for [(spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)] (17). Atoms Distance Atoms Distance C(48)-C(49) 1.386(6) C(57)-C(58) 1.383(5) C(49)-C(50) 1.374(7) C(58)-C(59) 1.373(6) C(50)-C(51) 1.373(6) C(59)-C(60) 1.365(6) C(51)-C(52) 1.404(5) O(2)-C(62') 1.31(2) C(52)-C(53) 1.466(5) O(2)-C(63) 1.594(17) C(53)-C(54) 1.341(5) O(2)-C(63') 1.35(3) C(54)-C(55) 1.469(5) O(2)-C(62) 1.581(17) C(55)-C(56) 1.408(5) C(61)-C(62) 1.404(19) C(55)-C(60) 1.404(5) C(63)-C(64) 1.44(8) C(56)-C(57) 1.390(5) C(61')-C(62') 1.50(2) C(63')-C(64') 1.50(8)
255
Table 51. Bond angles [°] for [(spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)] (17). Atoms Angle Atoms Angle C(1)-Ga(1)-C(15) 120.79(17) C(9)-Li(1)-Ga(1) 71.1(2) C(1)-Ga(1)-C(10) 105.97(15) C(8)-Li(1)-Ga(1) 79.0(3) C(15)-Ga(1)-C(10) 106.37(16) C(23)-Li(1)-Ga(1) 68.6(2) C(1)-Ga(1)-C(24) 105.06(16) O(2)-Li(2)-C(56) 133.1(5) C(15)-Ga(1)-C(24) 106.20(16) O(2)-Li(2)-C(42) 135.7(5) C(10)-Ga(1)-C(24) 112.63(16) C(56)-Li(2)-C(42) 91.1(3) C(1)-Ga(1)-Li(1) 112.3(3) O(2)-Li(2)-C(55) 110.1(4) C(15)-Ga(1)-Li(1) 126.9(3) C(56)-Li(2)-C(55) 33.05(17) C(10)-Ga(1)-Li(1) 57.7(2) C(42)-Li(2)-C(55) 107.7(4) C(24)-Ga(1)-Li(1) 55.5(2) O(2)-Li(2)-C(41) 111.6(4) C(47)-Ga(2)-C(33) 117.54(19) C(56)-Li(2)-C(41) 112.0(4) C(47)-Ga(2)-C(56) 106.96(16) C(42)-Li(2)-C(41) 32.92(18) C(33)-Ga(2)-C(56) 108.15(16) C(55)-Li(2)-C(41) 137.9(4) C(47)-Ga(2)-C(42) 106.01(18) O(2)-Li(2)-Ga(2) 178.4(6) C(33)-Ga(2)-C(42) 108.64(19) C(56)-Li(2)-Ga(2) 45.54(18) C(56)-Ga(2)-C(42) 109.33(15) C(42)-Li(2)-Ga(2) 45.70(18) C(47)-Ga(2)-Li(2) 123.7(3) C(55)-Li(2)-Ga(2) 69.1(2) C(33)-Ga(2)-Li(2) 118.8(3) C(41)-Li(2)-Ga(2) 69.4(2) C(56)-Ga(2)-Li(2) 54.8(2) C(6)-C(1)-C(2) 115.7(4) C(42)-Ga(2)-Li(2) 54.8(2) C(6)-C(1)-Ga(1) 120.6(3) O(1)-Li(1)-C(24) 131.5(5) C(2)-C(1)-Ga(1) 123.3(3) O(1)-Li(1)-C(10) 127.4(5) C(3)-C(2)-C(1) 123.5(4) C(24)-Li(1)-C(10) 92.6(3) C(4)-C(3)-C(2) 119.4(4) O(1)-Li(1)-C(9) 112.6(4) C(5)-C(4)-C(3) 119.8(4) C(24)-Li(1)-C(9) 115.7(4) C(4)-C(5)-C(6) 121.5(4) C(10)-Li(1)-C(9) 33.52(16) C(1)-C(6)-C(5) 120.1(4) O(1)-Li(1)-C(8) 114.6(5) C(1)-C(6)-C(7) 125.8(4) C(24)-Li(1)-C(8) 108.1(4) C(5)-C(6)-C(7) 114.1(4) C(10)-Li(1)-C(8) 61.3(2) C(8)-C(7)-C(6) 135.7(4) C(9)-Li(1)-C(8) 33.54(17) C(7)-C(8)-C(9) 132.5(4) O(1)-Li(1)-C(23) 102.7(4) C(7)-C(8)-Li(1) 105.5(4) C(24)-Li(1)-C(23) 32.16(17) C(9)-C(8)-Li(1) 69.6(3) C(10)-Li(1)-C(23) 106.5(4) C(10)-C(9)-C(14) 119.9(4) C(9)-Li(1)-C(23) 138.5(4) C(10)-C(9)-C(8) 123.7(4) C(8)-Li(1)-C(23) 140.2(4) C(14)-C(9)-C(8) 116.3(4) O(1)-Li(1)-Ga(1) 161.3(6) C(10)-C(9)-Li(1) 68.5(3) C(24)-Li(1)-Ga(1) 46.79(19) C(14)-C(9)-Li(1) 125.8(4) C(10)-Li(1)-Ga(1) 46.16(18) C(8)-C(9)-Li(1) 76.9(4)
256
Table 51 (con’t.). Bond angles [°] for [(spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)] (17). Atoms Angle Atoms Angle C(9)-C(10)-C(11) 116.1(4) C(30')-O(1)-C(31') 106.1(18) C(9)-C(10)-Ga(1) 123.6(3) C(30')-O(1)-C(31) 85.3(15) C(11)-C(10)-Ga(1) 119.9(3) C(31')-O(1)-C(31) 42.4(11) C(9)-C(10)-Li(1) 77.9(3) C(30')-O(1)-C(30) 23.8(18) C(11)-C(10)-Li(1) 124.1(4) C(31')-O(1)-C(30) 130.0(16) Ga(1)-C(10)-Li(1) 76.2(2) C(31)-O(1)-C(30) 103.7(13) C(12)-C(11)-C(10) 123.3(4) C(30')-O(1)-Li(1) 136.4(14) C(11)-C(12)-C(13) 119.3(4) C(31')-O(1)-Li(1) 116.7(13) C(14)-C(13)-C(12) 120.0(5) C(31)-O(1)-Li(1) 132.1(12) C(13)-C(14)-C(9) 121.4(4) C(30)-O(1)-Li(1) 113.0(10) C(20)-C(15)-C(16) 116.5(4) C(29)-C(30)-O(1) 115(3) C(20)-C(15)-Ga(1) 121.1(3) C(32)-C(31)-O(1) 99.0(18) C(16)-C(15)-Ga(1) 122.1(3) O(1)-C(30')-C(29') 104(2) C(17)-C(16)-C(15) 122.6(4) O(1)-C(31')-C(32') 111(3) C(18)-C(17)-C(16) 119.8(5) C(38)-C(33)-C(34) 116.4(5) C(19)-C(18)-C(17) 119.5(5) C(38)-C(33)-Ga(2) 122.7(4) C(18)-C(19)-C(20) 121.8(5) C(34)-C(33)-Ga(2) 120.8(4) C(19)-C(20)-C(15) 119.8(5) C(33)-C(34)-C(35) 123.2(6) C(19)-C(20)-C(21) 115.0(4) C(36)-C(35)-C(34) 118.7(7) C(15)-C(20)-C(21) 125.1(4) C(37)-C(36)-C(35) 120.2(7) C(22)-C(21)-C(20) 135.6(4) C(36)-C(37)-C(38) 122.0(7) C(21)-C(22)-C(23) 132.5(5) C(33)-C(38)-C(37) 119.4(6) C(24)-C(23)-C(28) 119.7(4) C(33)-C(38)-C(39) 125.6(5) C(24)-C(23)-C(22) 124.3(4) C(37)-C(38)-C(39) 114.9(6) C(28)-C(23)-C(22) 115.9(4) C(40)-C(39)-C(38) 135.8(6) C(24)-C(23)-Li(1) 60.3(3) C(39)-C(40)-C(41) 135.7(6) C(28)-C(23)-Li(1) 119.7(4) C(42)-C(41)-C(46) 119.8(5) C(22)-C(23)-Li(1) 91.9(4) C(42)-C(41)-C(40) 124.3(5) C(25)-C(24)-C(23) 117.0(4) C(46)-C(41)-C(40) 115.9(6) C(25)-C(24)-Ga(1) 120.5(3) C(42)-C(41)-Li(2) 64.1(3) C(23)-C(24)-Ga(1) 122.2(3) C(46)-C(41)-Li(2) 116.7(4) C(25)-C(24)-Li(1) 111.1(4) C(40)-C(41)-Li(2) 89.9(4) C(23)-C(24)-Li(1) 87.5(4) C(41)-C(42)-C(43) 115.8(4) Ga(1)-C(24)-Li(1) 77.7(3) C(41)-C(42)-Ga(2) 124.3(4) C(24)-C(25)-C(26) 122.0(4) C(43)-C(42)-Ga(2) 119.8(3) C(27)-C(26)-C(25) 120.4(5) C(41)-C(42)-Li(2) 83.0(4) C(28)-C(27)-C(26) 119.2(5) C(43)-C(42)-Li(2) 110.2(4) C(27)-C(28)-C(23) 121.6(5) Ga(2)-C(42)-Li(2) 79.5(2)
257
Table 51 (cont.). Bond angles [°] for [(spiro-[6,6]-bis-stilbenylgallium][Li(OEt2)] (17). Atoms Angle Atoms Angle C(44)-C(43)-C(42) 124.3(5) C(57)-C(56)-Ga(2) 120.1(3) C(43)-C(44)-C(45) 118.4(6) C(55)-C(56)-Ga(2) 123.9(3) C(46)-C(45)-C(44) 120.8(7) C(57)-C(56)-Li(2) 109.8(4) C(45)-C(46)-C(41) 120.8(7) C(55)-C(56)-Li(2) 83.8(4) C(48)-C(47)-C(52) 116.8(4) Ga(2)-C(56)-Li(2) 79.7(2) C(48)-C(47)-Ga(2) 121.4(3) C(58)-C(57)-C(56) 123.5(4) C(52)-C(47)-Ga(2) 121.4(3) C(57)-C(58)-C(59) 119.3(4) C(47)-C(48)-C(49) 123.1(5) C(60)-C(59)-C(58) 119.9(5) C(50)-C(49)-C(48) 119.6(5) C(59)-C(60)-C(55) 120.9(4) C(49)-C(50)-C(51) 119.0(5) C(62')-O(2)-C(63) 104.0(14) C(50)-C(51)-C(52) 121.9(5) C(62')-O(2)-C(63') 110.4(18) C(47)-C(52)-C(51) 119.4(4) C(63)-O(2)-C(63') 40.2(13) C(47)-C(52)-C(53) 126.4(4) C(62')-O(2)-C(62) 44.7(11) C(51)-C(52)-C(53) 114.2(4) C(63)-O(2)-C(62) 124.3(15) C(54)-C(53)-C(52) 136.4(4) C(63')-O(2)-C(62) 99.9(13) C(53)-C(54)-C(55) 134.6(4) C(62')-O(2)-Li(2) 122.8(13) C(56)-C(55)-C(60) 120.4(4) C(63)-O(2)-Li(2) 117.6(12) C(56)-C(55)-C(54) 124.0(4) C(63')-O(2)-Li(2) 126.8(16) C(60)-C(55)-C(54) 115.6(4) C(62)-O(2)-Li(2) 118.1(11) C(56)-C(55)-Li(2) 63.2(3) C(61)-C(62)-O(2) 109(2) C(60)-C(55)-Li(2) 115.2(3) C(64)-C(63)-O(2) 108(3) C(54)-C(55)-Li(2) 93.2(4) O(2)-C(62')-C(61') 107(3) C(57)-C(56)-C(55) 115.9(4) C(64')-C(63')-O(2) 99(3)
258
Structural Data for bis(gallepin)2.TMEDA (18)
Table 52. Crystal data and structural refinement for bis(gallepin)2.TMEDA (18)
Empirical formula C34 H36 Cl2 Ga2 N2
Formula weight 682.98
Temperature 273(2) K
Wavelength 0.71073 A
Crystal system, space group Monoclinic, C2/c
Unit cell dimensions a = 26.8548(10) A
b = 7.6807(3) A
c = 16.9633(6) A
alpha = 90 deg.
beta = 113.4040(10) deg.
gamma = 90 deg.
Volume 3211.0(2) A^3
Z, Calculated density 4, 1.413 Mg/m^3
Absorption coefficient 1.870 mm^-1
F(000) 1400
Crystal size 0.25 x 0.14 x 0.09 mm
Theta range for data collection 2.48 to 28.34 deg.
Limiting indices -35<=h<=35, -10<=k<=10, -22<=l<=22
Reflections collected / unique 21591 / 4018 [R(int) = 0.0301]
Completeness to theta = 28.34 99.90%
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.8498 and 0.6522
Refinement method Full-matrix least-squares on F^2
Data / restraints / parameters 4018 / 18 / 209
Goodness-of-fit on F^2 1.012
Final R indices [I>2sigma(I)] R1 = 0.0261, wR2 = 0.0642
R indices (all data) R1 = 0.0371, wR2 = 0.0693
Largest diff. peak and hole 0.377 and -0.251 e.A^-3
259
Table 53. Bond Lengths [Å] for bis(gallepin)2.TMEDA (18)
Atoms Distance Atoms Distance
Ga(1)-C(1) 1.9476(17) C(9)-C(10) 1.410(3)
Ga(1)-C(10) 1.9477(18) C(9)-C(14) 1.404(3)
Ga(1)-N(1) 2.1158(15) C(10)-C(11) 1.394(2)
Ga(1)-Cl(1) 2.2258(5) C(11)-C(12) 1.383(3)
C(1)-C(6) 1.408(3) C(12)-C(13) 1.377(3)
C(1)-C(2) 1.392(3) C(13)-C(14) 1.378(3)
C(2)-C(3) 1.387(3) N(1)-C(16') 1.432(15)
C(3)-C(4) 1.377(3) N(1)-C(17) 1.466(6)
C(4)-C(5) 1.369(3) N(1)-C(15) 1.506(4)
C(5)-C(6) 1.409(2) N(1)-C(15') 1.520(7)
C(6)-C(7) 1.465(3) N(1)-C(16) 1.526(6)
C(7)-C(8) 1.346(3) N(1)-C(17') 1.533(11)
C(8)-C(9) 1.475(3) C(15)-C(15)#1 1.499(9)
C(15')-C(15')#1 1.509(15)
260
Table 54. Bond angles [°] for bis(gallepin)2.TMEDA (18)
Atoms Angle Atoms Angle
C(1)-Ga(1)-C(10) 117.94(7) C(13)-C(12)-C(11) 119.28(19)
C(1)-Ga(1)-N(1) 104.64(6) C(14)-C(13)-C(12) 119.7(2)
C(10)-Ga(1)-N(1) 108.99(7) C(13)-C(14)-C(9) 121.9(2)
C(1)-Ga(1)-Cl(1) 110.47(6) C(16')-N(1)-C(17) 125.4(6)
C(10)-Ga(1)-Cl(1) 112.29(5) C(16')-N(1)-C(15) 80.5(4)
N(1)-Ga(1)-Cl(1) 100.79(5) C(17)-N(1)-C(15) 112.7(3)
C(6)-C(1)-C(2) 118.62(16) C(16')-N(1)-C(15') 112.5(5)
C(6)-C(1)-Ga(1) 121.03(13) C(17)-N(1)-C(15') 81.1(3)
C(2)-C(1)-Ga(1) 120.36(14) C(15)-N(1)-C(15') 35.6(3)
C(3)-C(2)-C(1) 121.8(2) C(16')-N(1)-C(16) 24.8(5)
C(2)-C(3)-C(4) 119.6(2) C(17)-N(1)-C(16) 108.5(4)
C(5)-C(4)-C(3) 119.89(18) C(15)-N(1)-C(16) 104.2(3)
C(4)-C(5)-C(6) 121.82(19) C(15')-N(1)-C(16) 132.3(4)
C(1)-C(6)-C(5) 118.28(17) C(16')-N(1)-C(17') 110.8(8)
C(1)-C(6)-C(7) 126.15(16) C(17)-N(1)-C(17') 23.9(4)
C(5)-C(6)-C(7) 115.53(17) C(15)-N(1)-C(17') 133.2(4)
C(8)-C(7)-C(6) 137.45(17) C(15')-N(1)-C(17') 104.6(5)
C(7)-C(8)-C(9) 137.93(18) C(16)-N(1)-C(17') 89.2(6)
C(10)-C(9)-C(14) 118.25(18) C(16')-N(1)-Ga(1) 109.1(5)
C(10)-C(9)-C(8) 126.41(17) C(17)-N(1)-Ga(1) 111.7(3)
C(14)-C(9)-C(8) 115.34(18) C(15)-N(1)-Ga(1) 114.03(18)
C(11)-C(10)-C(9) 118.31(17) C(15')-N(1)-Ga(1) 114.5(3)
C(11)-C(10)-Ga(1) 121.60(14) C(16)-N(1)-Ga(1) 104.9(2)
C(9)-C(10)-Ga(1) 120.09(13) C(17')-N(1)-Ga(1) 104.9(4)
C(12)-C(11)-C(10) 122.33(19) N(1)-C(15)-C(15)#1 112.9(5)
261
Structural Data for MesGaCl2(:L) (19)
Table 55. Crystal data and structural refinement for MesGaCl2(:L) (19)
Empirical formula C20H31Cl2GaN2
Formula weight 440.09
Temperature 273(2) K
Wavelength 0.71073 A
Crystal system, space group Triclinic, P-1
Unit cell dimensions a = 8.9728(6) Å
b = 9.1409(7) Å
c = 31.088(2) Å
= 87.0230(10)°
= 85.2090(10)°
= 61.5030(10)°
Volume 2232.9(3) Å3
Z, Calculated density 4, 1.309 Mg/m3
Absorption coefficient 1.477 mm-1
F(000) 920
Crystal size 0.45 x 0.42 x 0.15 mm
Theta range for data collection 2.54 to 28.40 deg.
Limiting indices -11<=h<=11, -12<=k<=12, -41<=l<=41
Reflections collected / unique 29671 / 11117 [R(int) = 0.0228]
Completeness to theta = 28.40 99.30%
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.8089 and 0.5562
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 11117 / 0 / 451
Goodness-of-fit on F^2 1.064
Final R indices [I>2sigma(I)] R1 = 0.0373, wR2 = 0.0992
R indices (all data) R1 = 0.0449, wR2 = 0.1031
Largest diff. peak and hole 0.468 and -0.777 e.A-3
262
Table 56. Bond Lengths [Å] for MesGaCl2(:L) (19)
Atoms Distance Atoms Distance
Ga(1)-C(1) 1.978(2) C(4)-C(8) 1.512(4)
Ga(1)-C(10) 2.048(2) C(5)-C(6) 1.395(3)
Ga(1)-Cl(2) 2.2444(6) C(6)-C(7) 1.509(4)
Ga(1)-Cl(1) 2.2468(6) C(11)-C(12) 1.350(3)
Ga(2)-C(21) 1.981(2) C(11)-C(17) 1.495(3)
Ga(2)-C(30) 2.043(2) C(12)-C(16) 1.496(3)
Ga(2)-Cl(4) 2.2478(6) C(13)-C(14) 1.520(4)
Ga(2)-Cl(3) 2.2449(6) C(13)-C(15) 1.523(4)
N(1)-C(10) 1.350(3) C(18)-C(19) 1.519(4)
N(1)-C(11) 1.393(3) C(18)-C(20) 1.532(4)
N(1)-C(18) 1.484(3) C(21)-C(26) 1.402(3)
N(2)-C(10) 1.350(3) C(21)-C(22) 1.415(3)
N(2)-C(12) 1.390(3) C(22)-C(23) 1.399(3)
N(2)-C(13) 1.484(3) C(22)-C(29) 1.510(3)
N(3)-C(30) 1.350(3) C(23)-C(24) 1.377(4)
N(3)-C(31) 1.392(3) C(24)-C(25) 1.377(4)
N(3)-C(38) 1.482(3) C(24)-C(28) 1.507(4)
N(4)-C(30) 1.355(3) C(25)-C(26) 1.402(3)
N(4)-C(32) 1.389(3) C(26)-C(27) 1.515(4)
N(4)-C(33) 1.491(3) C(31)-C(32) 1.350(4)
C(1)-C(2) 1.411(3) C(31)-C(37) 1.500(3)
C(1)-C(6) 1.411(3) C(32)-C(36) 1.494(4)
C(2)-C(3) 1.393(3) C(33)-C(34) 1.521(4)
C(2)-C(9) 1.514(3) C(33)-C(35) 1.530(4)
C(3)-C(4) 1.389(4) C(38)-C(40) 1.529(4)
C(4)-C(5) 1.375(4) C(38)-C(39) 1.521(4)
263
Table 57. Bond Angles [°] for MesGaCl2(:L) (19)
Atoms Angle Atoms Angle
C(1)-Ga(1)-C(10) 119.14(9) C(12)-C(11)-N(1) 106.67(19)
C(1)-Ga(1)-Cl(2) 114.96(7) C(12)-C(11)-C(17) 127.8(2)
C(10)-Ga(1)-Cl(2) 98.86(6) N(1)-C(11)-C(17) 125.4(2)
C(1)-Ga(1)-Cl(1) 109.34(7) C(11)-C(12)-N(2) 106.84(19)
C(10)-Ga(1)-Cl(1) 111.20(6) C(11)-C(12)-C(16) 127.5(2)
Cl(2)-Ga(1)-Cl(1) 101.71(3) N(2)-C(12)-C(16) 125.6(2)
C(21)-Ga(2)-C(30) 119.36(9) N(2)-C(13)-C(14) 111.8(2)
C(21)-Ga(2)-Cl(4) 108.49(7) N(2)-C(13)-C(15) 111.0(2)
C(30)-Ga(2)-Cl(4) 111.46(6) C(14)-C(13)-C(15) 113.7(2)
C(21)-Ga(2)-Cl(3) 115.93(7) N(1)-C(18)-C(19) 112.0(2)
C(30)-Ga(2)-Cl(3) 97.85(6) N(1)-C(18)-C(20) 111.1(2)
Cl(4)-Ga(2)-Cl(3) 102.26(3) C(19)-C(18)-C(20) 113.5(3)
C(10)-N(1)-C(11) 110.34(18) C(26)-C(21)-C(22) 117.9(2)
C(10)-N(1)-C(18) 122.96(18) C(26)-C(21)-Ga(2) 121.76(17)
C(11)-N(1)-C(18) 126.55(19) C(22)-C(21)-Ga(2) 120.27(17)
C(10)-N(2)-C(12) 110.37(18) C(23)-C(22)-C(21) 119.4(2)
C(10)-N(2)-C(13) 122.68(18) C(23)-C(22)-C(29) 118.3(2)
C(12)-N(2)-C(13) 126.82(18) C(21)-C(22)-C(29) 122.2(2)
C(30)-N(3)-C(31) 110.20(19) C(24)-C(23)-C(22) 122.5(2)
C(30)-N(3)-C(38) 122.65(19) C(25)-C(24)-C(23) 118.1(2)
C(31)-N(3)-C(38) 126.93(19) C(25)-C(24)-C(28) 120.3(3)
C(30)-N(4)-C(32) 110.06(19) C(23)-C(24)-C(28) 121.6(3)
C(30)-N(4)-C(33) 123.0(2) C(24)-C(25)-C(26) 121.5(2)
C(32)-N(4)-C(33) 126.8(2) C(21)-C(26)-C(25) 120.5(2)
C(2)-C(1)-C(6) 117.5(2) C(21)-C(26)-C(27) 122.5(2)
C(2)-C(1)-Ga(1) 120.59(16) C(25)-C(26)-C(27) 116.9(2)
C(6)-C(1)-Ga(1) 121.86(17) N(3)-C(30)-N(4) 105.90(18)
C(3)-C(2)-C(1) 120.3(2) N(3)-C(30)-Ga(2) 129.53(16)
C(3)-C(2)-C(9) 117.1(2) N(4)-C(30)-Ga(2) 123.81(15)
C(1)-C(2)-C(9) 122.5(2) C(32)-C(31)-N(3) 106.81(19)
C(2)-C(3)-C(4) 121.8(2) C(32)-C(31)-C(37) 127.9(2)
C(3)-C(4)-C(5) 117.9(2) N(3)-C(31)-C(37) 125.1(2)
C(3)-C(4)-C(8) 121.0(2) C(31)-C(32)-N(4) 107.0(2)
C(5)-C(4)-C(8) 121.0(2) C(31)-C(32)-C(36) 127.9(2)
C(4)-C(5)-C(6) 122.0(2) N(4)-C(32)-C(36) 125.0(2)
C(5)-C(6)-C(1) 120.4(2) N(4)-C(33)-C(34) 112.0(2)
C(5)-C(6)-C(7) 117.3(2) N(4)-C(33)-C(35) 110.7(2)
264
Table 57 (con’t). Bond Angles [°] for MesGaCl2(:L) (19)
Atoms Angle Atoms Angle
C(1)-C(6)-C(7) 122.3(2) C(34)-C(33)-C(35) 113.5(3)
N(2)-C(10)-N(1) 105.76(18) N(3)-C(38)-C(40) 111.4(2)
N(2)-C(10)-Ga(1) 129.87(15) N(3)-C(38)-C(39) 112.1(2)
N(1)-C(10)-Ga(1) 123.91(14) C(40)-C(38)-C(39) 113.6(2)
265
Structural Data for MesAlBr2(:L) (20)
Table 58. Crystal data and structural refinement for MesAlBr2(:L) (20) Empirical formula C20H31AlBr2N2 Formula weight 486.27 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, C2/c Unit cell dimensions a = 20.0676(11) Å b = 13.2261(7) Å c = 19.3315(16) Å = 90°
= 114.2240(10)°
= 90° Volume 4679.1(5) Å3 Z, Calculated density 8, 1.381 Mg/m3 Absorption coefficient 3.508 mm-1 F(000) 1984 Crystal size 0.43 x 0.30 x 0.10 mm Theta range for data collection 2.23 to 25.00 deg. Limiting indices -23<=h<=23, -15<=k<=15, -22<=l<=22 Reflections collected / unique 23975 / 4128 [R(int) = 0.0353] Completeness to theta = 25.00 100.00% Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7205 and 0.3139 Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 4128 / 0 / 226 Goodness-of-fit on F^2 1.032 Final R indices [I>2sigma(I)] R1 = 0.0361, wR2 = 0.0867 R indices (all data) R1 = 0.0487, wR2 = 0.0952 Largest diff. peak and hole 0.859 and -0.926 e.Å-3
266
Table 59. Bond Lengths [Å] for MesAlBr2(:L) (20)
Atoms Distance Atoms Distance
Al(1)-C(1) 1.989(3) C(2)-C(9) 1.513(5)
Al(1)-C(10) 2.050(3) C(3)-C(4) 1.379(5)
Al(1)-Br(1) 2.3364(10) C(4)-C(5) 1.376(5)
Al(1)-Br(2) 2.3373(10) C(4)-C(8) 1.518(5)
N(1)-C(10) 1.358(4) C(5)-C(6) 1.391(5)
N(1)-C(11) 1.386(4) C(6)-C(7) 1.521(5)
N(1)-C(18) 1.483(4) C(11)-C(12) 1.347(5)
N(2)-C(10) 1.357(4) C(11)-C(17) 1.499(5)
N(2)-C(12) 1.390(4) C(12)-C(16) 1.500(4)
N(2)-C(13) 1.479(4) C(13)-C(14) 1.516(6)
C(1)-C(2) 1.413(4) C(13)-C(15) 1.531(6)
C(1)-C(6) 1.418(5) C(18)-C(19) 1.514(5)
C(2)-C(3) 1.389(5) C(18)-C(20) 1.524(5)
267
Table 60. Bond Angles [°] for MesAlBr2(:L) (20)
Atoms Angle Atoms Angle
C(1)-Al(1)-C(10) 111.10(13) C(5)-C(4)-C(8) 121.2(4)
C(1)-Al(1)-Br(1) 109.43(9) C(3)-C(4)-C(8) 121.3(4)
C(10)-Al(1)-Br(1) 114.61(9) C(4)-C(5)-C(6) 122.0(3)
C(1)-Al(1)-Br(2) 119.11(10) C(5)-C(6)-C(1) 121.2(3)
C(10)-Al(1)-Br(2) 97.78(9) C(5)-C(6)-C(7) 117.6(3)
Br(1)-Al(1)-Br(2) 104.53(4) C(1)-C(6)-C(7) 121.2(3)
C(10)-N(1)-C(11) 110.8(2) N(2)-C(10)-N(1) 105.0(2)
C(10)-N(1)-C(18) 122.6(2) N(2)-C(10)-Al(1) 133.0(2)
C(11)-N(1)-C(18) 126.5(3) N(1)-C(10)-Al(1) 121.9(2)
C(10)-N(2)-C(12) 110.4(2) C(12)-C(11)-N(1) 106.7(3)
C(10)-N(2)-C(13) 123.3(3) C(12)-C(11)-C(17) 127.4(3)
C(12)-N(2)-C(13) 126.2(3) N(1)-C(11)-C(17) 125.8(3)
C(2)-C(1)-C(6) 115.9(3) C(11)-C(12)-N(2) 107.1(3)
C(2)-C(1)-Al(1) 125.7(2) C(11)-C(12)-C(16) 127.2(3)
C(6)-C(1)-Al(1) 118.4(2) N(2)-C(12)-C(16) 125.6(3)
C(3)-C(2)-C(1) 121.1(3) N(2)-C(13)-C(14) 111.9(3)
C(3)-C(2)-C(9) 117.1(3) N(2)-C(13)-C(15) 111.3(4)
C(1)-C(2)-C(9) 121.7(3) C(14)-C(13)-C(15) 113.3(3)
C(4)-C(3)-C(2) 122.3(3) N(1)-C(18)-C(19) 111.2(3)
C(5)-C(4)-C(3) 117.4(3) N(1)-C(18)-C(20) 111.3(3)
C(19)-C(18)-C(20) 114.3(3)
268
Structural Data for [MesInBr2(:L)][InBr3(:L)] (21)
Table 61. Crystal data and structural refinement for [MesInBr2(:L)][InBr3(:L)] (21)
Empirical formula C31H51Br5In2N4
Formula weight 1108.95
Temperature 273(2) K
Wavelength 0.71073 Å
Crystal system, space group Triclinic, P-1
Unit cell dimensions a = 9.6832(15) Å
b = 10.9013(17) Å
c = 20.164(3) Å
= 95.520(3)°
= 99.865(3)°
= 95.363(3)°
Volume 2074.2(6) A3
Z, Calculated density 2, 1.776 Mg/m3
Absorption coefficient 5.952 mm-1
F(000) 1076
Crystal size 0.17 x 0.11 x 0.04 mm
Theta range for data collection 2.25 to 25.00 deg.
Limiting indices -11<=h<=11, -12<=k<=12, -23<=l<=23
Reflections collected / unique 16339 / 7294 [R(int) = 0.0894]
Completeness to theta = 25.00 99.80%
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.7967 and 0.4310
Refinement method Full-matrix least-squares on F^2
Data / restraints / parameters 7294 / 0 / 379
Goodness-of-fit on F^2 1
Final R indices [I>2sigma(I)] R1 = 0.0581, wR2 = 0.1209
R indices (all data) R1 = 0.1541, wR2 = 0.1522
Largest diff. peak and hole 1.303 and -0.926 e.A-3
269
Table 62. Bond Lengths [Å] for [MesInBr2(:L)][InBr3(:L)] ,(21)
Atoms Angle Atoms Angle
In(1)-C(12) 2.170(13) C(14)-C(15) 1.429(18)
In(1)-C(1) 2.224(10) C(15)-C(16) 1.349(18)
In(1)-Br(2) 2.5365(16) C(15)-C(19) 1.494(17)
In(1)-Br(1) 2.5630(17) C(16)-C(17) 1.392(17)
N(1)-C(1) 1.332(13) C(17)-C(18) 1.520(17)
N(1)-C(2) 1.397(13) In(2)-C(21) 2.175(10)
N(1)-C(9) 1.504(13) In(2)-Br(4) 2.4847(17)
N(2)-C(1) 1.333(13) In(2)-Br(5) 2.4928(18)
N(2)-C(3) 1.391(13) In(2)-Br(3) 2.4966(16)
N(2)-C(4) 1.477(14) N(3)-C(21) 1.344(12)
C(2)-C(3) 1.332(16) N(3)-C(22) 1.397(12)
C(2)-C(8) 1.511(16) N(3)-C(29) 1.479(13)
C(3)-C(7) 1.496(16) N(4)-C(21) 1.360(12)
C(4)-C(5) 1.480(16) N(4)-C(23) 1.400(13)
C(4)-C(6) 1.538(16) N(4)-C(24) 1.464(13)
C(9)-C(11) 1.499(15) C(22)-C(23) 1.321(14)
C(9)-C(10) 1.536(15) C(22)-C(28) 1.502(14)
C(12)-C(13) 1.385(16) C(23)-C(27) 1.498(15)
C(12)-C(17) 1.427(16) C(24)-C(25) 1.512(16)
C(13)-C(20) 1.307(17) C(24)-C(26) 1.528(17)
C(13)-C(14) 1.472(18) C(29)-C(31) 1.497(18)
C(29)-C(30) 1.535(16)
270
Table 63. Bond Angles [°] for [MesInBr2(:L)][InBr3(:L)] (21)
Atoms Angle Atoms Angle
C(12)-In(1)-C(1) 119.1(4) C(16)-C(15)-C(14) 115.6(13)
C(12)-In(1)-Br(2) 119.0(3) C(16)-C(15)-C(19) 124.5(14)
C(1)-In(1)-Br(2) 102.0(3) C(14)-C(15)-C(19) 119.7(14)
C(12)-In(1)-Br(1) 109.9(3) C(15)-C(16)-C(17) 123.6(14)
C(1)-In(1)-Br(1) 102.8(3) C(16)-C(17)-C(12) 120.3(13)
Br(2)-In(1)-Br(1) 101.66(6) C(16)-C(17)-C(18) 117.2(13)
C(1)-N(1)-C(2) 109.0(10) C(12)-C(17)-C(18) 122.6(12)
C(1)-N(1)-C(9) 124.6(9) C(21)-In(2)-Br(4) 115.3(3)
C(2)-N(1)-C(9) 126.4(10) C(21)-In(2)-Br(5) 110.2(3)
C(1)-N(2)-C(3) 109.9(10) Br(4)-In(2)-Br(5) 107.08(7)
C(1)-N(2)-C(4) 122.8(9) C(21)-In(2)-Br(3) 109.2(3)
C(3)-N(2)-C(4) 127.3(11) Br(4)-In(2)-Br(3) 108.74(6)
N(1)-C(1)-N(2) 107.2(9) Br(5)-In(2)-Br(3) 106.02(6)
N(1)-C(1)-In(1) 125.6(8) C(21)-N(3)-C(22) 110.4(9)
N(2)-C(1)-In(1) 127.1(8) C(21)-N(3)-C(29) 122.4(9)
C(3)-C(2)-N(1) 107.5(10) C(22)-N(3)-C(29) 127.1(9)
C(3)-C(2)-C(8) 126.7(12) C(21)-N(4)-C(23) 109.6(9)
N(1)-C(2)-C(8) 125.8(12) C(21)-N(4)-C(24) 122.3(9)
C(2)-C(3)-N(2) 106.4(10) C(23)-N(4)-C(24) 128.1(9)
C(2)-C(3)-C(7) 127.9(12) N(3)-C(21)-N(4) 105.5(9)
N(2)-C(3)-C(7) 125.5(13) N(3)-C(21)-In(2) 130.6(8)
N(2)-C(4)-C(5) 114.3(11) N(4)-C(21)-In(2) 124.0(7)
N(2)-C(4)-C(6) 110.7(10) C(23)-C(22)-N(3) 107.1(9)
C(5)-C(4)-C(6) 112.3(12) C(23)-C(22)-C(28) 127.7(10)
C(11)-C(9)-N(1) 112.7(10) N(3)-C(22)-C(28) 125.1(10)
C(11)-C(9)-C(10) 112.6(11) C(22)-C(23)-N(4) 107.4(9)
N(1)-C(9)-C(10) 110.9(9) C(22)-C(23)-C(27) 128.4(12)
C(13)-C(12)-C(17) 121.1(13) N(4)-C(23)-C(27) 124.2(11)
C(13)-C(12)-In(1) 120.5(10) N(4)-C(24)-C(25) 112.5(11)
C(17)-C(12)-In(1) 118.4(10) N(4)-C(24)-C(26) 110.1(10)
C(20)-C(13)-C(12) 121.5(16) C(25)-C(24)-C(26) 115.4(12)
C(20)-C(13)-C(14) 123.7(14) N(3)-C(29)-C(31) 111.9(11)
C(12)-C(13)-C(14) 114.6(13) N(3)-C(29)-C(30) 111.7(11)
C(15)-C(14)-C(13) 124.5(13) C(31)-C(29)-C(30) 114.7(11)
271
Structural Data for [MesGaCl(:L)]2 (22)
Table 64. Crystal data and structural refinement for [MesGaCl(:L)]2 (22) Empirical formula C40H62Cl2Ga2N4
Formula weight 809.28
Temperature 273(2) K
Wavelength 0.71073 Å
Crystal system, space group Monoclinic, P2(1)/c
Unit cell dimensions a = 15.0926(19) Å
c = 20.160(3) Å
b = 14.3561(19) Å
= 90°
= 103.844(2)°
= 90°
Volume 4241.2(9) A3
Z, Calculated density 4, 1.267 Mg/m3
F(000) 1704
Crystal size 0.14 x 0.11 x 0.05 mm
Theta range for data collection 2.08 to 25.00 deg.
Limiting indices -17<=h<=17, -17<=k<=17, -23<=l<=23
Reflections collected / unique 44092 / 7454 [R(int) = 0.1737]
Completeness to theta = 25.00 100.00%
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.9321 and 0.8252
Refinement method Full-matrix least-squares on F^2
Data / restraints / parameters 7454 / 0 / 433
Goodness-of-fit on F^2 1.025
Final R indices [I>2sigma(I)] R1 = 0.0570, wR2 = 0.1235
R indices (all data) R1 = 0.1683, wR2 = 0.1766
Largest diff. peak and hole 0.524 and -0.585 e.Å-3
272
Table 65. Bond Distances [Å] for [MesGaCl(:L)]2 (22)
Atoms Distance Atoms Distance
Ga(1)-C(12) 2.028(7) C(9)-C(11) 1.523(10)
Ga(1)-C(1) 2.101(7) C(12)-C(17) 1.391(10)
Ga(1)-Cl(1) 2.300(2) C(12)-C(13) 1.414(10)
Ga(1)-Ga(2) 2.4474(11) C(13)-C(14) 1.383(10)
Ga(2)-C(32) 2.014(7) C(13)-C(20) 1.526(10)
Ga(2)-C(21) 2.084(7) C(14)-C(15) 1.373(12)
Ga(2)-Cl(2) 2.324(2) C(15)-C(16) 1.371(11)
N(1)-C(1) 1.345(8) C(15)-C(19) 1.528(11)
N(1)-C(2) 1.383(9) C(16)-C(17) 1.400(10)
N(1)-C(9) 1.488(9) C(17)-C(18) 1.516(10)
N(2)-C(1) 1.350(8) C(22)-C(23) 1.336(10)
N(2)-C(3) 1.401(9) C(22)-C(28) 1.500(10)
N(2)-C(4) 1.477(9) C(23)-C(27) 1.510(10)
N(3)-C(21) 1.356(8) C(24)-C(25) 1.536(10)
N(3)-C(22) 1.381(8) C(24)-C(26) 1.521(10)
N(3)-C(29) 1.476(9) C(29)-C(31) 1.519(10)
N(4)-C(21) 1.347(8) C(29)-C(30) 1.530(10)
N(4)-C(23) 1.404(9) C(32)-C(33) 1.424(9)
N(4)-C(24) 1.490(9) C(32)-C(37) 1.417(9)
C(2)-C(3) 1.362(11) C(33)-C(34) 1.355(10)
C(2)-C(8) 1.487(11) C(33)-C(40) 1.511(10)
C(3)-C(7) 1.475(11) C(34)-C(35) 1.388(11)
C(4)-C(6) 1.503(11) C(35)-C(36) 1.371(10)
C(4)-C(5) 1.518(11) C(35)-C(39) 1.513(11)
C(9)-C(10) 1.508(11) C(36)-C(37) 1.393(9)
C(37)-C(38) 1.531(10)
273
Table 66. Bond Angles [°] for [MesGaCl(:L)]2 (22)
Atoms Angle Atoms Angle
C(12)-Ga(1)-C(1) 106.7(3) C(13)-C(12)-Ga(1) 121.2(6)
C(12)-Ga(1)-Cl(1) 103.8(2) C(12)-C(13)-C(14) 120.9(8)
C(1)-Ga(1)-Cl(1) 105.7(2) C(12)-C(13)-C(20) 122.5(7)
C(12)-Ga(1)-Ga(2) 132.2(2) C(14)-C(13)-C(20) 116.5(7)
C(1)-Ga(1)-Ga(2) 101.59(19) C(15)-C(14)-C(13) 122.1(8)
Cl(1)-Ga(1)-Ga(2) 104.64(6) C(16)-C(15)-C(14) 117.9(8)
C(32)-Ga(2)-C(21) 103.0(3) C(16)-C(15)-C(19) 121.1(9)
C(32)-Ga(2)-Cl(2) 108.2(2) C(14)-C(15)-C(19) 121.0(9)
C(21)-Ga(2)-Cl(2) 95.2(2) C(15)-C(16)-C(17) 121.5(8)
C(32)-Ga(2)-Ga(1) 117.1(2) C(12)-C(17)-C(16) 121.3(7)
C(21)-Ga(2)-Ga(1) 122.57(19) C(12)-C(17)-C(18) 122.1(7)
Cl(2)-Ga(2)-Ga(1) 108.12(7) C(16)-C(17)-C(18) 116.7(7)
C(1)-N(1)-C(2) 112.0(7) N(4)-C(21)-N(3) 104.6(6)
C(1)-N(1)-C(9) 122.1(6) N(4)-C(21)-Ga(2) 125.0(5)
C(2)-N(1)-C(9) 125.8(7) N(3)-C(21)-Ga(2) 130.4(5)
C(1)-N(2)-C(3) 110.7(6) C(23)-C(22)-N(3) 106.7(7)
C(1)-N(2)-C(4) 121.7(6) C(23)-C(22)-C(28) 127.3(7)
C(3)-N(2)-C(4) 127.5(7) N(3)-C(22)-C(28) 125.9(7)
C(21)-N(3)-C(22) 111.4(6) C(22)-C(23)-N(4) 106.8(6)
C(21)-N(3)-C(29) 122.4(6) C(22)-C(23)-C(27) 128.5(8)
C(22)-N(3)-C(29) 125.9(6) N(4)-C(23)-C(27) 124.7(7)
C(21)-N(4)-C(23) 110.5(6) N(4)-C(24)-C(25) 111.3(7)
C(21)-N(4)-C(24) 123.1(6) N(4)-C(24)-C(26) 111.1(6)
C(23)-N(4)-C(24) 126.3(6) C(25)-C(24)-C(26) 113.6(7)
N(2)-C(1)-N(1) 104.9(6) N(3)-C(29)-C(31) 112.3(6)
N(2)-C(1)-Ga(1) 130.8(5) N(3)-C(29)-C(30) 112.9(6)
N(1)-C(1)-Ga(1) 124.2(5) C(31)-C(29)-C(30) 111.8(7)
C(3)-C(2)-N(1) 106.0(7) C(33)-C(32)-C(37) 115.7(7)
C(3)-C(2)-C(8) 127.8(8) C(33)-C(32)-Ga(2) 124.3(6)
N(1)-C(2)-C(8) 126.2(9) C(37)-C(32)-Ga(2) 119.8(5)
C(2)-C(3)-N(2) 106.4(7) C(34)-C(33)-C(32) 120.8(8)
C(2)-C(3)-C(7) 127.3(9) C(34)-C(33)-C(40) 118.7(7)
N(2)-C(3)-C(7) 126.2(9) C(32)-C(33)-C(40) 120.4(7)
N(2)-C(4)-C(6) 112.4(7) C(33)-C(34)-C(35) 122.9(8)
N(2)-C(4)-C(5) 112.5(7) C(36)-C(35)-C(34) 117.4(7)
C(6)-C(4)-C(5) 111.5(7) C(36)-C(35)-C(39) 120.2(9)
N(1)-C(9)-C(10) 113.0(7) C(34)-C(35)-C(39) 122.4(8)
274
Table 66 con’t. Bond Angles [°] for [MesGaCl(:L)]2 (22)
Atoms Angle Atoms Angle
N(1)-C(9)-C(11) 112.4(7) C(35)-C(36)-C(37) 121.6(8)
C(10)-C(9)-C(11) 112.1(7) C(36)-C(37)-C(32) 120.9(7)
C(17)-C(12)-C(13) 116.4(7) C(36)-C(37)-C(38) 118.3(7)
C(17)-C(12)-Ga(1) 122.4(6) C(32)-C(37)-C(38) 120.7(7)
275
Structural Data for Mes4Ga6(:L)2 (23)
Table 67. Crystal data and structural refinement for Mes4Ga6(:L)2 (23)
Empirical formula C72H100Ga6N4
Formula weight 1439.88
Temperature 273(2) K
Wavelength 0.71073 Å
Crystal system, space group Orthorhombic, Fddd
Unit cell dimensions a = 19.6044(13) Å
b = 22.9053(15) Å
c = 32.804(2) Å
= 90
= 90 deg.deg
= 90 deg.
Volume 14730.6(17) Å3
Z, Calculated density 8, 1.299 Mg/m3
Absorption coefficient 2.203 mm-1
F(000) 5968
Crystal size 0.13 x 0.11 x 0.05 mm
Theta range for data collection 2.17 to 26.00 deg.
Limiting indices -24<=h<=24, -28<=k<=28, -40<=l<=40
Reflections collected / unique 41534 / 3633 [R(int) = 0.1157]
Completeness to theta = 26.00 100.00%
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.8978 and 0.7627
Refinement method Full-matrix least-squares on F^2
Data / restraints / parameters 3633 / 3 / 241
Goodness-of-fit on F^2 1.049
Final R indices [I>2sigma(I)] R1 = 0.0570, wR2 = 0.1483
R indices (all data) R1 = 0.1176, wR2 = 0.1814
Largest diff. peak and hole 0.491 and -0.383 e.Å-3
276
Table 68. Bond Distances [Å] for Mes4Ga6(:L)2 (23)
Atoms Distance Atoms Distance
Ga(1)-C(1) 1.966(11) C(8)-C(9) 1.38(3)
Ga(1)-Ga(3) 2.5109(12) C(8)-C(13')#3 1.540(18)
Ga(1)-Ga(3)#1 2.5109(12) C(9)-C(10) 1.36(3)
Ga(1)-Ga(2)#2 2.5905(11) C(10)-C(11) 1.35(3)
Ga(1)-Ga(2) 2.5905(11) C(10)-C(14) 1.54(2)
Ga(2)-C(7) 1.955(11) C(11)-C(12) 1.44(2)
Ga(2)-Ga(3) 2.5165(12) C(12)-C(13) 1.528(18)
Ga(2)-Ga(3)#1 2.5165(12) C(13')-C(8)#3 1.540(18)
Ga(2)-Ga(1)#2 2.5905(11) N(1)-C(15) 1.355(9)
Ga(3)-C(15) 1.982(11) N(1)-C(16) 1.399(9)
Ga(3)-Ga(1)#2 2.5109(12) N(1)-C(18) 1.481(10)
Ga(3)-Ga(2)#2 2.5165(12) C(15)-N(1)#2 1.355(9)
C(1)-C(2) 1.422(10) C(16)-C(16)#2 1.347(16)
C(1)-C(2)#1 1.422(10) C(16)-C(17) 1.511(11)
C(2)-C(3) 1.382(12) C(18)-C(19) 1.484(14)
C(2)-C(6) 1.495(13) C(18)-C(20) 1.526(14)
C(3)-C(4) 1.393(12) C(21)-C(22) 1.39
C(4)-C(3)#1 1.393(12) C(21)-C(26) 1.39
C(4)-C(5) 1.491(17) C(21)-C(27) 1.57(2)
C(7)-C(8)#3 1.369(19) C(22)-C(23) 1.39
C(7)-C(8) 1.369(19) C(23)-C(24) 1.39
C(7)-C(12) 1.536(19) C(24)-C(25) 1.39
C(7)-C(12)#3 1.536(19) C(25)-C(26) 1.39
277
Table 69. Bond Angles [°] for Mes4Ga6(:L)2 (23)
Atoms Angle Atoms Angle
C(1)-Ga(1)-Ga(3) 136.72(3) C(8)-C(7)-Ga(2) 124.7(8)
C(1)-Ga(1)-Ga(3)#1 136.72(3) C(12)-C(7)-Ga(2) 114.2(7)
Ga(3)-Ga(1)-Ga(3)#1 86.56(5) C(12)#3-C(7)-Ga(2) 114.2(7)
C(1)-Ga(1)-Ga(2)#2 134.88(3) C(7)-C(8)-C(9) 124.9(15)
Ga(3)-Ga(1)-Ga(2)#2 59.09(3) C(7)-C(8)-C(13')#3 113(2)
Ga(3)#1-Ga(1)-Ga(2)#2 59.09(3) C(9)-C(8)-C(13')#3 119(2)
C(1)-Ga(1)-Ga(2) 134.88(3) C(7)-C(8)-C(13)#3 104.2(17)
Ga(3)-Ga(1)-Ga(2) 59.09(3) C(9)-C(8)-C(13)#3 123.0(19)
Ga(3)#1-Ga(1)-Ga(2) 59.09(3) C(10)-C(9)-C(8) 122.9(18)
Ga(2)#2-Ga(1)-Ga(2) 90.24(5) C(10)-C(9)-C(12)#3 127.1(16)
C(7)-Ga(2)-Ga(3) 136.84(3) C(9)-C(10)-C(11) 118.7(16)
C(7)-Ga(2)-Ga(3)#1 136.84(3) C(9)-C(10)-C(14) 125(2)
Ga(3)-Ga(2)-Ga(3)#1 86.32(5) C(11)-C(10)-C(14) 116(2)
C(7)-Ga(2)-Ga(1)#2 135.12(3) C(11)-C(10)-C(24) 121(2)
Ga(3)-Ga(2)-Ga(1)#2 58.88(3) C(10)-C(11)-C(12) 119.0(18)
Ga(3)#1-Ga(2)-Ga(1)#2 58.88(3) C(10)-C(11)-C(8)#3 104.3(17)
C(7)-Ga(2)-Ga(1) 135.12(3) C(13')-C(12)-C(11) 113(2)
Ga(3)-Ga(2)-Ga(1) 58.88(3) C(11)-C(12)-C(13) 113(2)
Ga(3)#1-Ga(2)-Ga(1) 58.88(3) C(13')-C(12)-C(7) 113(2)
Ga(1)#2-Ga(2)-Ga(1) 89.76(5) C(11)-C(12)-C(7) 121.9(15)
C(15)-Ga(3)-Ga(1)#2 133.28(3) C(13)-C(12)-C(7) 124.0(19)
C(15)-Ga(3)-Ga(1) 133.28(3) C(15)-N(1)-C(16) 109.6(6)
Ga(1)#2-Ga(3)-Ga(1) 93.44(5) C(15)-N(1)-C(18) 123.2(7)
C(15)-Ga(3)-Ga(2) 133.16(3) C(16)-N(1)-C(18) 127.1(7)
Ga(1)#2-Ga(3)-Ga(2) 62.03(3) N(1)#2-C(15)-N(1) 106.5(9)
Ga(1)-Ga(3)-Ga(2) 62.03(3) N(1)#2-C(15)-Ga(3) 126.8(4)
C(15)-Ga(3)-Ga(2)#2 133.16(3) N(1)-C(15)-Ga(3) 126.8(4)
Ga(1)#2-Ga(3)-Ga(2)#2 62.03(3) C(16)#2-C(16)-N(1) 107.1(4)
Ga(1)-Ga(3)-Ga(2)#2 62.03(3) C(16)#2-C(16)-C(17) 128.7(5)
Ga(2)-Ga(3)-Ga(2)#2 93.68(5) N(1)-C(16)-C(17) 124.1(7)
C(2)-C(1)-C(2)#1 116.9(11) C(19)-C(18)-N(1) 110.3(8)
C(2)-C(1)-Ga(1) 121.6(5) C(19)-C(18)-C(20) 114.7(9)
C(2)#1-C(1)-Ga(1) 121.6(5) N(1)-C(18)-C(20) 112.7(9)
C(3)-C(2)-C(1) 120.1(9) C(22)-C(21)-C(26) 120
C(3)-C(2)-C(6) 119.3(9) C(22)-C(21)-C(27) 76(6)
C(1)-C(2)-C(6) 120.6(8) C(26)-C(21)-C(27) 164(6)
C(2)-C(3)-C(4) 123.7(10) C(21)-C(22)-C(23) 120
278
Table 2.69. Bond Angles [°] for Mes4Ga6(:L)2 (23)
Atoms Angle Atoms Angle C(3)-C(4)-C(3)#1 115.4(12) C(22)-C(23)-C(24) 120 C(3)-C(4)-C(5) 122.3(6) C(25)-C(24)-C(23) 120 C(3)#1-C(4)-C(5) 122.3(6) C(25)-C(24)-C(10) 130(6) C(8)-C(7)-C(12) 107.3(11) C(23)-C(24)-C(10) 110(6) C(8)#3-C(7)-C(12)#3 107.3(11) C(24)-C(25)-C(26) 120 C(8)#3-C(7)-Ga(2) 124.7(8) C(25)-C(26)-C(21) 120
279
Structural Data for glyoxal-bis-(1-adamantyl)imine (24)
Table 70. Crystal data and structural refinement for glyoxal-bis-(1-adamantyl)imine (24) Empirical formula C22H32N2 Formula weight 324.5 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, C2/c Unit cell dimensions a = 11.5780(8) Å b = 6.9162(8) Å c = 23.232(2) Å = 90°
= 90.027(2)°
= 90°
Volume 1860.3(3) A3 Z, Calculated density 4, 1.159 Mg/m3 Absorption coefficient 0.067 mm-1 F(000) 712 Crystal size 0.40 x 0.35 x 0.30 mm Theta range for data collection 3.43 to 26.00 deg.
Limiting indices -14<=h<=14, -8<=k<=8, -28<=l<=28
Reflections collected / unique 10311 / 1835 [R(int) = 0.0261] Completeness to theta = 26.00 99.90%
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.9801 and 0.9736 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 1835 / 0 / 110 Goodness-of-fit on F^2 1.068 Final R indices [I>2sigma(I)] R1 = 0.0497, wR2 = 0.1192 R indices (all data) R1 = 0.0556, wR2 = 0.1243 Extinction coefficient 0.0230(18) Largest diff. peak and hole 0.161 and -0.257 e.A-3
280
Table 71. Bond Distances [Å] for glyoxal-bis-(1-adamantyl)imine (24) Atoms Distance Atoms Distance N(1)-C(1) 1.2592(16) C(4)-C(5) 1.526(2) N(1)-C(2) 1.4691(15) C(4)-C(10) 1.525(2) C(1)-C(1)#1 1.466(2) C(5)-C(6) 1.526(2) C(2)-C(7) 1.5376(17) C(6)-C(7) 1.5305(18) C(2)-C(3) 1.5295(17) C(6)-C(11) 1.525(2) C(2)-C(8) 1.5323(18) C(8)-C(9) 1.5292(18) C(3)-C(4) 1.5323(17) C(9)-C(11) 1.524(2) C(9)-C(10) 1.525(2)
Table 72. Bond Angles [°] for glyoxal-bis-(1-adamantyl)imine (24) Atoms Angle Atoms Angle C(1)-N(1)-C(2) 121.69(11) C(3)-C(4)-C(10) 109.31(12) N(1)-C(1)-C(1)#1 120.18(15) C(4)-C(5)-C(6) 109.46(11) N(1)-C(2)-C(7) 107.11(10) C(7)-C(6)-C(5) 109.15(11) N(1)-C(2)-C(3) 116.27(9) C(7)-C(6)-C(11) 109.39(12) C(7)-C(2)-C(3) 109.00(11) C(5)-C(6)-C(11) 109.76(12) N(1)-C(2)-C(8) 106.98(10) C(6)-C(7)-C(2) 110.20(10) C(7)-C(2)-C(8) 108.09(10) C(9)-C(8)-C(2) 110.37(10) C(3)-C(2)-C(8) 109.10(10) C(11)-C(9)-C(10) 109.45(13) C(4)-C(3)-C(2) 110.03(10) C(11)-C(9)-C(8) 109.18(12) C(5)-C(4)-C(3) 109.38(12) C(10)-C(9)-C(8) 109.55(11) C(5)-C(4)-C(10) 109.82(12) C(9)-C(10)-C(4) 109.57(11) C(9)-C(11)-C(6) 109.63(10)
281
Structural Data for Arduengo’s Carbene (26)
Table 73. Crystal data and structural refinement for Arduengo’s Carbene (26) Empirical formula C23H32N2 Formula weight 336.51 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/c Unit cell dimensions a = 7.5954(5) Å b = 19.7470(12) Å c = 12.8016(8) Å = 90°
= 106.5400(10)°
= 90°
Volume 1840.6(2) Å3 Z, Calculated density 4, 1.214 Mg/m3 Absorption coefficient 0.070 mm-1 F(000) 736 Crystal size 0.30 x 0.17 x 0.08 mm Theta range for data collection 2.65 to 30.19 deg.
Limiting indices -10<=h<=10, -27<=k<=27, -18<=l<=18
Reflections collected / unique 28547 / 5462 [R(int) = 0.0388] Completeness to theta = 30.19 99.90% Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9944 and 0.9792 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 5462 / 0 / 226 Goodness-of-fit on F^2 1.009 Final R indices [I>2sigma(I)] R1 = 0.0485, wR2 = 0.1217 R indices (all data) R1 = 0.0803, wR2 = 0.1422 Largest diff. peak and hole 0.296 and -0.187 e.Å-3
282
Table 74. Bond Distances [Å] for Arduengo’s Carbene (26) Atoms Distance Atoms Distance N(1)-C(1) 1.3624(16) C(8)-C(9) 1.5343(18) N(1)-C(2) 1.3851(16) C(10)-C(11) 1.532(2) N(1)-C(14) 1.4814(16) C(11)-C(12) 1.5317(19) N(2)-C(1) 1.3661(16) C(11)-C(13) 1.528(2) N(2)-C(3) 1.3843(16) C(14)-C(22) 1.5286(17) N(2)-C(4) 1.4841(15) C(14)-C(15) 1.5345(17) C(2)-C(3) 1.3384(19) C(14)-C(19) 1.5333(17) C(4)-C(5) 1.5353(17) C(15)-C(16) 1.5318(18) C(4)-C(9) 1.5343(17) C(16)-C(23) 1.527(2) C(4)-C(12) 1.5297(18) C(16)-C(17) 1.527(2) C(5)-C(6) 1.5353(18) C(17)-C(18) 1.526(2) C(6)-C(13) 1.534(2) C(18)-C(20) 1.528(2) C(6)-C(7) 1.5293(19) C(18)-C(19) 1.5311(19) C(7)-C(8) 1.5280(19) C(20)-C(21) 1.530(2) C(8)-C(10) 1.522(2) C(21)-C(23) 1.526(2) C(21)-C(22) 1.5331(19)
283
Table 75. Bond Angles [°] for Arduengo’s Carbene (26) Atoms Angle Atoms Angle C(1)-N(1)-C(2) 112.00(11) C(10)-C(11)-C(12) 109.63(12) C(1)-N(1)-C(14) 124.60(10) C(10)-C(11)-C(13) 109.77(12) C(2)-N(1)-C(14) 123.14(10) C(12)-C(11)-C(13) 109.12(11) C(1)-N(2)-C(3) 112.19(11) C(11)-C(12)-C(4) 109.95(10) C(1)-N(2)-C(4) 122.29(10) C(6)-C(13)-C(11) 109.29(11) C(3)-N(2)-C(4) 125.49(10) N(1)-C(14)-C(22) 110.34(10) N(1)-C(1)-N(2) 102.62(10) N(1)-C(14)-C(15) 109.20(10) C(3)-C(2)-N(1) 106.82(11) C(22)-C(14)-C(15) 108.65(10) C(2)-C(3)-N(2) 106.38(11) N(1)-C(14)-C(19) 110.45(10) N(2)-C(4)-C(5) 109.38(10) C(22)-C(14)-C(19) 109.24(10) N(2)-C(4)-C(9) 110.50(10) C(15)-C(14)-C(19) 108.93(10) C(5)-C(4)-C(9) 108.75(10) C(14)-C(15)-C(16) 109.86(10) N(2)-C(4)-C(12) 109.90(10) C(23)-C(16)-C(17) 109.35(12) C(5)-C(4)-C(12) 108.86(10) C(23)-C(16)-C(15) 109.26(12) C(9)-C(4)-C(12) 109.43(10) C(17)-C(16)-C(15) 109.65(12) C(4)-C(5)-C(6) 109.92(10) C(18)-C(17)-C(16) 109.73(12) C(13)-C(6)-C(7) 109.64(11) C(17)-C(18)-C(20) 109.61(12) C(13)-C(6)-C(5) 109.70(11) C(17)-C(18)-C(19) 108.87(11) C(7)-C(6)-C(5) 109.06(11) C(20)-C(18)-C(19) 109.89(12) C(8)-C(7)-C(6) 109.19(11) C(18)-C(19)-C(14) 110.21(11) C(7)-C(8)-C(10) 110.35(12) C(21)-C(20)-C(18) 109.02(11) C(7)-C(8)-C(9) 109.74(11) C(20)-C(21)-C(23) 109.46(13) C(10)-C(8)-C(9) 108.91(11) C(20)-C(21)-C(22) 110.03(12) C(8)-C(9)-C(4) 109.75(10) C(23)-C(21)-C(22) 109.38(11) C(11)-C(10)-C(8) 109.38(11) C(14)-C(22)-C(21) 109.88(11) C(16)-C(23)-C(21) 109.45(11
284
APPENDIX B
RESEARCH PUBLICATIONS
Co-Authored by Brandon Quillian
1. Wang, Y.; Quillian, B.; Wei, P.; Yang, X.-J.; Robinson, G. H., New Pb-Pb bonds: “Syntheses and molecular structures of hexabiphenyldiplumbane and tri(trisbiphenylplumbyl)plumbate”, Chem. Commun. 2004, 2224-2225.
2. Yang, X.-J.; Quillian, B.; Wang, Y.; Wei, P.; Robinson, G. H., “A Metallocene with Ga-Zr
Bonds: Cp2Zr(GaR)2 (Cp = C5H5; R = -C6H3-2,6-(2,4,6-iPr3C6H2)2)”, Organometallics 2004, 23, 5119-5120.
3. Wang, Y.; Quillian, B.; Wei, P; Wang, H.; Yang, X.-J.; Xie, Y.; King, R. B.; Schleyer, P. v.
R.; Schaefer, H. F. III; Robinson, G. H., “On the Chemistry of Zn-Zn Bonds, RZn-ZnR (R = [{2,6-Pr2
iC6H3)N(Me)C}2CH]): Synthesis, Structure, and Computations”, J. Am. Chem. Soc. 2005, 127, 11944-11945.
4. Wang, Y.; Quillian, B.; Yang, X.-J.; Wei, P.; Chen, Z.; Wannere, C. S.; Schleyer, P. v. R.;
Robinson, G. H., “A Metallocene-Complexed Dibismuthene: Cp2Zr(BiR)2 (Cp = C5H5;R = C6H3-2,6-Mes2)”, J. Am. Chem. Soc. 2005, 127, 7672-7673.
5. Yang, X.-J.; Wang, Y.; Quillian, B.; Wei, P.; Chen, Z.; Schleyer, P. v. R.; Robinson, G. H.,
“Syntheses, Structures and Bonding of Cp2M(ER)2 (Cp = C5H5; M = Ti, Zr; E = Ga, In; R = -C6H3-2,6-(2,4,6-iPr3C6H2)2)”, Organometallics 2006, 25, 925-929.
6. Yang, X.-J.; Wang, Y.; Wei, P.; Quillian, B.; Robinson, G. H., “Syntheses and structures of
new diaryl lead(II) compounds PbR2 (1, R = 2,4,6-triphenyl; 2, R = 2,6-bis(1’-naphthyl)phenyl)”, Chem. Commun. 2006, 403-405.
7. Quillian, B.; Wang, Y.; Wei, P.; Handy, A.; Robinson, G. H., “2,6-Di(4-t-
butylphenyl)phenyl-group 13 Organometallic Compounds”, J. Organomet. Chem. 2006, 691, 3765-3770.
8. Wang, Y.; Quillian, B.; Wei, P.; Wannere, C. S.; Schleyer, P. v. R.; Robinson, G. H., “A
Self-Assembled Organometallic Sphere: [{t-BuC5H4)(t-BuC5H3)Zr(μ-H)Na}2]4”, Organometallics 2006, 25, 3286-3288.
285
9. Wang, Y.; Quillian, B.; Wannere, C. S.; Wei, P.; Schleyer, P. v. R.; Robinson, G. H., “A Trimetallic Compound Containing Zn-Zr bonds: Cp2Zr(ZnR)2 (Cp = C5H5;R = -C6H3-2,6-(2,4,6-i-Pr3C6H2)2)”, Organometallics 2007, 26, 3054-3056.
10. Wang, Y.; Quillian, B.; Wei, P.; Wannere, C. S.; Xie, Y.; King, R. B.; Schaefer, H. F.
III; Schleyer, P. v. R.; Robinson, G. H., “A Stable Neutral Diborene Containing a B=B Double Bond”, J. Am. Chem. Soc. 2007, 129 12412-12413.
11. Quillian, B.; Wang, Y.; Wei, P.; Wannere, C. S.; Schleyer, P. v. R.; Robinson, G. H.,
“Gallepins. Neutral Gallium Analogues of the Tropylium Ion: Synthesis, Structure, and Aromaticity”, J. Am. Chem. Soc. 2007, 129, 13380-13381.
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