1

Coordination Modes of Hydroxylamine Ligands

at Elements Through the Periodic Table

WESTFÄLISCHEWILHELMS-UNIVERSITÄT

MÜNSTER

Norbert W. Mitzel

UNIVERSITÄT

BIELEFELD

2

Gas electron diffraction

@ MS (soon BI)RaphaelBerger

3

BeLi B C N O F Ne

He

Na

K

Rb

Cs

Fr

Mg

Ca

Sr

Ba

Ra

Sc

Y

La

Ac

Ti

Zr

Hf

Rf

V

Nb

Ta

Db

Cr

Mo

W

Sg

Mn

Tc

Re

Bh

Fe

Ru

Os

Hs

Co

Rh

Ir

Mt

Ni

Pd

Pt

__

Cu

Ag

Au

__

Zn

Cd

Hg

__

Al

Ga

In

Tl

Si

Ge

Sn

Pb

P

As

Sb

Bi

S

Se

Te

Po

Cl

Br

I

At

Ar

Kr

Xe

Rn

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Yb LuTm

H

Th U Np Pu Am Cm Bk Cf Es Fm No LrMdPa

43 5 6 7 8 9 10

2

11

19

37

55

87

12

20

38

56

88

21

39

57

89

22

40

72

104

23

41

73

105

24

42

74

106

25

43

75

107

26

44

76

108

27

45

77

109

28

46

78

110

29

47

79

111

30

48

80

112

13

31

49

81

14

32

50

82

15

33

51

83

16

34

52

84

17

35

53

85

18

36

54

86

58 59 60 61 62 63 64 65 66 67 68 70 7169

1

90 92 93 94 95 96 97 98 99 100 102 10310191

1Ia

2IIa

3IIIb

4IVb

5Vb

6VIb

7VIIb

8 9VIIIb

10 11Ib

12IIb

13IIIa

14IVa

15Va

16VIa

17VIIa

18VIIIa

Overview

114

E-O-NR2

4

XRDsolid

77.1(1)1.963(1)

74.1(1)1.904(2)

GEDgas

94.3(9)2.273(17)

79.4(6)2.011(17)

Å, °

<SiONd(Si···N)

<SiONd(Si···N)

F3SiONMe2

F3CF2SiONMe2

SiF

FF

O

N C

C

P21/nmp. -69°C

Si

F

FF

O

NC

CF

F

C

1.912 Å

Pnmamp. -43°C

F3SiONMe2 / (F3C)F2SiONMe2

* Mitzel, Losehand, Wu, Cremer, Rankin, J. Am. Chem. Soc. 2000, 122, 4471# Mitzel, Vojinović, Fröhlich, Foerster, Rankin, J. Am. Chem. Soc. 2005, 127, 13705

5

Si

O

N

C

FF

F2

F

F

C

Si

N

O

MP2/6-311++G(d,p)

(F3C)F2SiONMe2 – electron density

6

[4+4]-Coordination in SiON compounds

SiN

O

N.W. Mitzel, A.J. Blake, D.W.H. Rankin, J. Am. Chem. Soc. 1997, 119, 4143

Si(ONMe2)4

109.1(av)°

7

O

H3GeONMe2

GeN

C‘

C

<GeON104.6(1)105.2(5)°

Ge···N 2.601(1)2.587(6) Å

Me2O-96°C

Me2NOLi + H3GeBr H3GeONMe2 + LiBr

XRD GEDsolid gas

Pnmam.p. -22°C

Decomp. > -20°C :

H-H2Ge-ONMe2 →→→→

HONMe2 + (GeH2)∞∞∞∞

Decomp. > -20°C :

H-H2Ge-ONMe2 →→→→

HONMe2 + (GeH2)∞∞∞∞

N.W. Mitzel, U. Losehand, S.L. Hinchley, D.W.H. Rankin, Inorg. Chem. 2001, 40, 661

8

O‘ C

C‘N

<OSnC‘108.1(6)→→→→118.1(av)°

<OSnC‘108.1(6)→→→→118.1(av)°

<SnON102.5(8) →→→→101.5(4)°

<SnON102.5(8) →→→→101.5(4)°

GED → XRDgas → solid

Sn O

Me3SnONMe2

<OSnC99.6(10)→→→→99.7(4)°

<OSnC99.6(10)→→→→99.7(4)°

O

Sn N

O‘

N. W. Mitzel, U. Losehand, A. D. Richardson, Organometallics 1999, 18, 2610

2.745(9) Å

C‘

CC‘‘

mp. -85°CP2/n

2.998(10) ÅO

Sn N

O

Sn N

9

Al

N

Al O

OOAl

N

N 96.4° 88.0°

86.5°

AlO

N

Al

O

N

140.8°102.7°

Ga

GaN

N

O

O

GaGa

N

N

O

O

107.7(5)° 131.1(5)°

Hausen,Schmöger,Schwarz,J. Organomet. Chem.

1978, 153, 271

(Me2GaONMe2)2

(tBu2AlONMe2)2(Me2AlONMe2)3

(tBu2GaONMe2)2

N. W. Mitzel, C. Lustig, M. Woski, Dalton Trans. 2004, 397

MR3 + HONMe2 RH + ⅛ [R2M-ONMe2]nn

(M = Al, Ga)

10

P21/n

2.33

2(4)

GaO

N

[HONMe]2CH2 as ligand

M = Al, Ga

MM

N

O

NO

BuLi-BuH -LiCl

-MeH

Me2MCl

GaMe3

N

OLi

N

OLi

N

OH

N

OH

N. W. Mitzel, C. Lustig, Angew. Chem. 2001, 113, 4521

11

AlAl

Al

N O

O

O

O

N

N

NCP1

[HONMe]2CH2 as ligand

N. W. Mitzel, C. Lustig, Angew. Chem. 2001, 113, 4521

O

AlO O

O

Al

Al

N

N

N

N

Me

N

Al

O

O O

Al

N

N

Al

O

N

Me

-MeHAlMe3

N

OH

N

OH

B3LYP/6-31G(d):∆E = 5 kJ/mol

1H-NMR:-80°C → +20°Cdynamic system

12Patrick Bösing, 2006

OO N

R

OH

H+

NR

OH

NR

OH

R = Me, tBu, Ph

ON

N

O

Ga

Ga

C C

CC

C

C

NR

O

NR

ONaBH4

Me3Ga

[HON(R)CH2]2 as ligand

O

N

NO

Ga

Ga

CO

NO

NC

H HP1

C2/c

N

N

OGa

OGa

Bu

Bu

BuBu

ONH

N

OH

tBu3Ga

t t

t

t

⊕⊕⊕⊕-

13

Zn

C

O

O

O

N

NN C

ZnZn

Zn

Zn

Zn(ZnR)4(ONMe2)6

C2/c

M. Ullrich, C. Lustig, R. J. F. Berger, N. W. Mitzel, Eur. J. Inorg. Chem. 2006, 4219

N OH + 5 ZnMe26

- 6 CH4

N

Zn

O

O

O

N

Zn

ZnZn

Zn

Pccn

O

ON

N

N

N OH + 5 ZniPr26

- 6 C3H8

∆T ZnOPyrolysis / Ar

14Matthias Ullrich, 200660 40 20 0 δ / ppm70 50 30 10

VT-13C-NMR –[Zn(ZnEt)4(ONEt2)6]

H2C(NEt2)13C{1H}-NMR,

C7D8, RT

13C{1H}-DEPT-135C7D8, -70°C

H3C(NEt2)

H3C(ZnEt)

H2C(ZnEt)

R = R‘ = Et

15

→ 3 x change = full period

6 O−N ligands, C2-symmetry

[Zn(ZnEt)4(ONEt2)6] - molecular dynamics

Matthias Ullrich, 2005R. J. F. Berger, 2006

für [Zn(ZnMe)4(ONMe2)6]:DFT(BP)/SV(P): ∆E = 5.4 kcal / mol

16S. Jana, R. Fröhlich, N. W. Mitzel, Chem. Eur. J. 2006, 12, 592

4 Me2N-NH2 + 4 ZnEt2

- 4 C2H6Zn

N N

Zn

Zn

Zn

N

N

NN

N

NN

ZnZn

ZnN N

ZnEt

NMe2

NHHN

N

Me2N

Me2

Me2

Et

Et

H

Et

N

ZnZn

ZnN N

Zn

N

NN

N

N

> 350°CZn3N2

(ZnEt)4[N(H)NMe2]4

P21/n

Zn(CN2)

∆T / Ar

17

Zn(ZnMe)4[N(H)NMe2]2(ONEt2)4

Mixed zinc-hydrazide/hydroxylamide

5 ZnMe2 + 2 H2NNMe2 + 4 HONEt2

- 6 CH4

N

Zn

Zn

Zn

N

N

N

N

O

NZn

ZnN

O

O

NYield 87 %mp. 164 °C (dec.)IR [KBr, cm-1]: 3184 (br, N-H)

Pbca

S. Jana, R. Fröhlich, R. J. F. Berger, N. W. Mitzel, Chem. Commun. 2006, 3993.

C24H66N6O4Zn5

18Alexander Willner, 2006/7

ON-Ligands in CVD precursors

Ti(NMe2)4

RN

O

MR 4

• M = Ti, Zr; R = Et: Wieghardt et al. Z. Anorg. Allg. Chem. 1982, 490, 182

• M = Ti, Zr, Hf; R = Me: Mitzel, Blake, Rankin, J. Chem. Soc. Dalton Trans. 1996, 2089

- 4 HNMe2

Yield: 72%; EA: �; MS: m/z = 284 1H NMR: 2.85 s, 3.29 m; 13C-NMR: 48.5, 55.7

Hf(ONEt2)4 HfO2

• A. C. Jones et al. J. Chem. Mater. 2004, 14, 3101 & Chem. Vap. Depos. 2003, 9, 309

Liquid InjectionMOCVD

NR

OH

NR

OHTiO

N

N

O

High-κ-Dielectrics

Subl. 60°C / 10-2 mbar

19

Ti

C

C

O

CC

O

N

C

NC

C

NR

OH

NR

OH

R = Me, tBu, Ph

Yield.: 78%, EA: �MS: m/z = 301 [M+ - Me]1H NMR: -0.06, 1.97, 2.41, 2.4313C NMR: 10.9, 26.2, 46.6, 60.0,117.9

Pbca

Ti-O: 1.911 / 1.936(3) ÅTi-N: 2.109 / 2.132(3) ÅTi-C: 2.172(4) Å

TiMe3

-2 CH4

ON-Ligands in polymerisation catalysts

Cp*TiCl3, 3 MeLi

-2 CH4

Alexander Willner, 2006

20Ajay Venugopal, 2006

K{Y[ON(iPr)2]}4

YCl3K[ON(iPr)2] THF

HON(iPr)2

KH -H2; THF Y

OON

NNO O

KK

Yield: 73%, EA: �;1H NMR: 1.10, 3.08; 13C NMR: 20.4, 54.7

21

MCl3, THFK[ONEt2]HONEt2

KH-H2; THF

Cp*(ONEt2)M-[µ2(O)-η2-ONEt2]2-M(ONEt2)Cp*

M = Y, La, Ho, Er, Lu

Er Er

N

N

N

N

O

O

O

O

Organolanthanoid complexes

Ajay Venugopal, 2006

NaCp*, -KCl

Er-O 2.136Er-N 2.415

Er-N 2.417

2.2682.304

22

{Be2[ON(iPr)2]4}

BeCl2Et2O

HON(iPr)2 LiON(iPr)2 {Be2[ON(iPr)2]4}n-BuLi

Et2O

Raphael J. F. Berger, Surajit Jana, 2006

O O

O

N

NN

N

O

Be

Be

113.4°

110.1°

126.8°

113.9°

23

K[ONMe2]HONMe2KH HONMe2

insoluble

K[ONMe2][HONMe2]

Potassium aggregates

K

O

N

K

O

N

K

O

N

KO

N

K O

O

O

OO

O

O

NN

K

THFTHF soluble

-H2; THF

Ajay Venugopal, 2007

24

K2

K2‘ K1‘

K1O2N2 O4

N4

O1

N1 O3N3

O10(THF)

K[ONiPr2]HONiPr2KH

-H2; THFHONMe2

insoluble [K(iPr2NO-H-ONiPr2)(THF)]

THF soluble

Potassium aggregates

Ajay Venugopal, 2007

THF

25

O

K

NO

K

N

O K

N

O

O

O

OK

N

O

K

NK

N

THF

THF

THF

OTHF

{[K6[ON(CH2Ph)2]6(THF)4}

Ajay Venugopal, 2007

26

M

O

N

Metal hydroxylamine compounds

• different bridging and binding modes

• hemilabile ligands

• flexible coordination and aggregation modi

M

ON

M M

O

N

MSi, Ge, SnTi, Zr, Hf

------------ K, Y, La, Sm, Ho, Er, Lu -----------

-------- Al, Ga, In, Zn, Cd ------

27

Fabian

Conrady

Patrick

Bösing

Ajay

Venugopal

Alexander

Willner

Michael

Hagemann

Raphael

Berger

Benjamin

Hellmann

Ingo

Gronde

Matthias

Ullrich

Denise

Defayay

Constantin

Sicking

Ulf

Strasser

Ina

Kamps

Jasmin

Chmiel