prelims, contents pages

Contents

Seyyed Javad Sabounchei,Fateme Akhlaghi Bagherjeri,Colette Boskovic, Robert W. Gable,Roya Karamian and Mostafa Asadbegy

Polyhedron 53 (2013) 1

Reactivity of mercury(II) halides with the a-ketostabilized sulfonium ylides: Crystal structures oftwo new polymer and binuclear complexes and invitro antibacterial study

Reaction of a-keto stabilized sulfoniumylides (Me)2SCHC(O)C6H4R (R = p-NO2 andp-Br) with HgX2 (X = Cl, Br and I) leads to

binuclear and polymer products of the type[HgX2(Ylide)]2 and [{HgI(Ylide)]n. The infra-red, NMR data and the X-ray crystal struc-tures of the complexes 1 and 2 demonstrateC-coordination of the ylide to the metal andpresence of the asymmetric halide-bridgedbinuclear and the zig-zag polymeric chainstructures, respectively. In addition, theantibacterial effects of the DMSO-solutionsof the complexes were investigated by discdiffusion method against three Gram posi-tive and three negative bacteria.

Irvin N. Booysen, Thulani Hlela,Thomas I.A. Gerber, Orde Q. Munro andMatthew P. Akerman


Novel vanadium compounds with 2-pyridyl-benzimidazole

The coordination behaviour of Hpybz (2-pyridylbenzimidazole) towards vanadiumin various oxidation states (i.e. +III/IV/V)has been explored. A novel binuclearmixed-valence oxovanadium compound,(l-O)[VVO(pybz)2ÆVIVO(Hpybz)(acac)], wasobtained from the reaction of Hpybz withVO(acac)2. ESR analysis illustrates para-magnetic behaviour, typical of a type Idimer.

Mehdi Araghi and Forough Bokaei


Manganese(III) porphyrin supported on multi-wall carbon nanotubes: A highly efficient andreusable biomimetic catalyst for oxidative dec-arboxylation of a-arylcarboxylic acids and oxi-dation of alkanes with sodium periodate

Highly efficient oxidative decarboxylationof carboxylic acids and also oxidation ofalkanes with sodium periodate catalyzedby tetrakis(p-aminophenyl)porphyrinato-manganese(III) chloride, [Mn(TNH2PP)Cl],supported on functionalized multi-wallcarbon nanotubes, MWCNT, is reported.This heterogenized catalyst could be re-used several times without significant lossof its catalytic activity.

R

R'COOH

H [Mn(TNH2PP)Cl@MWCNT]

NaIO4, Imidazole, CH3CN/ H2Oor or

R'

R

O

R R'R R'

O

R R'

OH

+

+

CO2

Elsevier Ltd.

Polyhedron 53, 10 April 2013

Contents lists available at SciVerse ScienceDirect

Polyhedron

journal homepage: www.elsevier .com/locate /poly

Aleksander Kufelnicki,Magdalena Wozniczka,Urszula Kalinowska-Lis, Julia Jezierskaand Justyn Ochocki


Synthesis, acid–base and complexing propertieswith Cu(II), Co(II) and Zn(II) in aqueous solutionof a novel 1H-benzimidazol-2-ylmethyl diethylphosphate ligand: Comparison with other2-substituted benzimidazole ligands

A novel 1H-benzimidazol-2-ylmethyldiethyl phosphate (2-BimOpe) derivativeshows specific coordinating properties to-wards Cu(II), Co(II) and Zn(II) in aqueoussolution as compared with other 2-sub-stituted benzimidazoles. The differencescome evidently from a bulky effect ofthe estrificated phosphoric group and itselectron withdrawing effect.

Ireneusz Kownacki, Maciej Kubicki andPaulina Bła _zejewska-Chadyniak


Synthesis and crystal structures of binucleariridium and rhodium complexes with symme-trical and unsymmetrical bulky siloxide bridges

The article presents synthesis and structur-al studies of two isostructural rhodium andiridium complexes such as [{Rh(cod)}2

(l-OSiMe3)(l-OSi(OSiMe3)3)] (1) and [{Ir(cod)}2(l-OSiMe3)(l-OSi(OSiMe3)3)] (2) ob-tained by sequential reaction of appropri-ate TM chloride precursors ([{M(l-Cl)(cod)}2], M = Rh, Ir) with different bulkysodium siloxides as well as iridium com-plex with two identical hindered bridgingsiloxide ligands: [{Ir(cod)(l-OSi(OSiMe3)3)}2](3).

Aloke Kumar Ghosh, Antonio Bauzá,Valerio Bertolasi, Antonio Frontera andDebashis Ray


Dinuclear and heptanuclear nickel(II) com-plexes: Anion coordination induced ligand armhydrolysis and aggregation around a nickel(II)core

Water derived in situ generation of hydro-xido anions lead to self-assembly of fourphenoxido-based Schiff base ligated [Ni2]fragments around a central NiII cationproviding a novel heptanuclear nickel(II)complex.

Humberto C. Garcia, Renata Diniz andLuiz Fernando C. de Oliveira


Supramolecular architectures of metal com-plexes containing 4-sulfobenzoate dianion and1,2-bis(4-pyridyl)ethane

Four Mn(II), Co(II), Ni(II) and Zn(II) com-plexes with multidentate organic acid andnitrogen ligand have been obtained. For themanganese complex was observed a dif-ferent coordination, where only the 4-sulfobenzoate ions are bonded, whereasfor all the other compounds the 1,2-bis-(4-pyridyl)ethane is also coordinated. For allthe compounds, hydrogen bonds, C–H� � �pand p-stacking are the major forces drivingthe solid state arrangement.

vContents

Manas Sutradhar, Tannistha Roy Barman,Julia Klanke, Michael G.B. Drew andEva Rentschler


A novel Cu(II) dimer containing oxime-hydra-zone Schiff base ligands with an unusual modeof coordination: Study of magnetic, autoreduc-tion and solution properties

A new hydrazone based Schiff base ligand,3-methylpyrazole-5-carbohydrazone of2,3-butanedione monoxime (HL), and itsCu(II) (1) and Co(III) (2) complexes are

reported. The ligand shows an unusualmode of coordination. Complex 1 is a dimercontaining a crystallographic centre ofsymmetry and is found to undergo dis-sociation and autoreduction transforma-tion in solvents such as DMF and DMSO.The EPR spectrum of 1 in DMF shows thepartial dissociation of the binuclear com-plex into a mononuclear species. Magneticstudies of 1 show that the two Cu(II)centres are strongly antiferromagneticallycoupled via bridging N–O groups.

Leah C. Matsinha, Selwyn F. Mapolie andGregory S. Smith


Synthesis and characterization of mono- andbinuclear iminopyridyl and salicylaldimineRu(II)–arene complexes

A series of mono- and binuclear rutheniu-m(II)–arene iminopyridyl and salicylaldi-mine Schiff-base complexes have beensynthesized and characterised by NMRand IR spectroscopies, ESI-mass spectro-metry, and elemental analyses. The mole-cular structure of a representativemononuclear complex was determined byX-ray diffraction analysis.

Joseph D. Henthorn, Netra Mishra,Christopher D. Haun, Ana L. Castro,Hunter G. Douglas, Matthew Pegram,Brian Stadelmaier, Jay S. Huebner andChristos Lampropoulos


Using single-molecule magnets as analyte-re-cognition compounds in photo-electric chemicalsensors: Recent results from [Mn12O12(O2-CCH3)16(H2O)4]Æ2CH3COOHÆ4H2O, and [Mn12-O12(O2CPh)16(H2O)4]

The single-molecule magnets [Mn12O12-(O2CCH3)16(H2O)4]Æ2CH3COOHÆ4H2O, and[Mn12O12(O2CPh)16(H2O)4] were investi-gated as analyte-recognition compounds(ARCs) on photo-electric chemical sensors(PECS). The data for these sensors wereparticularly encouraging both for the vaporand the liquid analytes considered, andcontinued investigations may lead to sen-sors using molecular clusters as ARCs withhigh sensitivity and analyte specificity.

Dorel Oltean, Alpar Pöllnitz andAnca Silvestru


Organophosphorus ligands with XPNSO skele-ton (X = O, S) and their Pd(II) complexes.Crystal and molecular structure of [{XP(OE-t)2}(O2SR)]NH (X = O, R = Me, Ph; X = S, R =C6H4Cl-4) and Pd[{SP(OEt)2}(O2SC6H4Cl-4)N]2

Several organophosphorus acids of type[{XP(OEt)2}(O2SR)]NH [X = O, R = Me, Ph,C6H4CH3-4; X = S, R = C6H4Cl-4], as well astheir potassium salts K[{XP(OEt)2}(O2SR)N]and the palladium(II) complexesPd[{XP(OEt)2}(O2SR)N]2 were preparedand structurally characterized. Single-crys-tal X-ray diffraction studies revealed eithermonomeric or polymeric structures withdifferent degrees of association in case ofthe free acids. A trans-S,N-coordinationpattern of the organophosphorus ligandwas found in the palladium complexPd[{SP(OEt)2}(O2SC6H4Cl-4)N]2.

vi Contents

Zeinab Moradi-Shoeili, Zahra Amini,Davar M. Boghaei and Behrouz Notash


Synthesis, X-ray structure and ascorbic oxida-tion properties of ternary a-amino acid Schiffbase-bipy Cu(II) complexes as functional mod-els for ascorbic oxidase

Three new ternary copper(II) complexeshave been prepared and characterized.Synthesized compounds are found to becatalytically active in oxidation of ascorbicacid in presence of dioxygen which modelsthe ascorbate oxidation property of theCu(II) sites in ascorbate oxidase.

B. Machura and I. Gryca


Synthesis, spectroscopic characterization, X-raystructure and DFT calculations of p-tolylimidorhenium(V) complexes of 2,2¢-dipyridylamine

The paper concerns two novel imido rhenium(V) complexes [Re(p-NC6H4CH3)Cl(OMe)(Hdpa)(PPh3)]ReO4 (1) and [Re(p-NC6H4CH3)Br(OMe)(Hdpa)-(PPh3)]ReO4 (2). The compounds havebeen synthesized and characterised spectrosco-pically and structurally (by single-crystal X-raydiffraction). The experimental studies on 1 havebeen accompanied computationally by the den-sity functional theory (DFT) and time-dependentDFT calculations. Additional information aboutthe Re–NR bond characteristics in [Re(p-NC6-H4CH3)Cl(OMe)(dpa)(PPh3)]+ was obtained byNBO analysis.

Saeed Dehghanpour, Ali Mahmoudi,Lila Najafi, Mohammad Khalafbeigi andKhadijeh Jahani


[MII(3-(2¢-pyridylmethyleneamino)pyridine)(NO3)2], (M = Co, Zn, Cd) coordination poly-mers; single, mixed and composite crystals

3-(2¢-Pyridylmethyleneamino)pyridine andits homo and heterometallic coordinationpolymers have been synthesized and char-acterized. A series of composite crystalsbased on epitaxial growth were prepared.Thermal and fluorescence properties ofligand and complexes have been studiedand compared.

Ting Zhang, Yun-Qian Zhang,Qian Jiang Zhu and Zhu Tao


Supramolecular assemblies based on the inter-action of a copper dication with alky-substi-tuted cucurbit[6]urils

In the present study, we describe theinteraction of copper cations with alkyl-substituted cucurbiturils (SQ[6])s in theabsence and presence of a third species.The corresponding supramolecular assem-blies are dependent upon the addition ofthe third species.

viiContents

Young Jae Lee and Soon W. Lee


Ligands containing pyridyl-carboxylate term-inals and their discrete silver and polymericcadmium compounds: (n-py)–CH@N–C10H6–COOH (n = 2 (HL1), 3 (HL2)), [Ag(HL1)2](PF6),[Ag(HL1)2](NO3)(H2O), and [Cd(L2)2]¥

Two potential linking ligands containingpyridyl-carboxylate terminals {(n-py)–CH@N–C10H6–COOH (n = 2 (HL1), 3 (HL2)}were synthesized. By employing the li-gands, two discrete Ag(I) complexes,[Ag(HL1)2](PF6) and [Ag(HL1)2](NO3)(H2O),and a 3D cadmium coordination polymer,[Cd(L2)2]¥, were prepared. Ligand HL1 ex-hibited a red-shift on complex formation.

HL1

COOHN

AgPF6

MeOH, 12 h

N

HOOCN NAg

AgNO3

MeOH, 16 hN NAg

N NHOOC

HOOC

(PF6)

(NO3)

Hai-Wei Kuai, Xiao-Chun Cheng andXiao-Hong Zhu


Four cadmium(II) coordination polymers withan N- and O-donor ligand: Structural character-ization, in situ reaction and fluorescent prop-erty

Hydrothermal reactions of 5-(1H-benzo-triazol-1-ylmethyl)isophthalic acid (H2L)with Cd(II) salt under different experimen-tal conditions provide four complexes withdifferent structures varying from 1D to 3D.The L2) ligands in the complexes are foundto show a variety of coordination modes.The results of this study illustrate thestructural diversity of complexes underdifferent experimental conditions.

Ekaterina F. Zhilina, Dmitrii L. Chizhov,Aleksey A. Sidorov,Grigory G. Aleksandrov, Mikhail Kiskin,Pavel A. Slepukhin, Matvey Fedin,Denis V. Starichenko,Alexandr V. Korolev, Yuri N. Shvachko,Igor L. Eremenko andValeriy N. Charushin


Neutral tetranuclear Cu(II) complex of 2,6-di(5-trifluoromethylpyrazol-3-yl)pyridine: Synth-esis, characterization and its transformationwith selected aza-ligands

The first grid-like tetranuclear Cu(II) com-plex with fluoro containing 2,6-di(3-pyr-azolyl)pyridine ligand was synthesized.Transformations of the complex with se-lected aza-ligands were realized.

B. Machura, J. Palion, J. Mrozinski,B. Kalinska, M. Amini, M.M. Najafpourand R. Kruszynski


Manganese(II) complexes of 2,3,5,6-tetra-(2-pyridyl)pyrazine – Syntheses, crystal structures,spectroscopic, magnetic and catalytic properties

Several novel manganese(II) complexes of2,3,5,6-tetra(2-pyridyl)pyrazine have beensynthesised and characterised by means ofelemental analysis, IR, EPR, magnetic mea-surements and single crystal X-ray analy-

sis. Two of them, [Mn(NO3)2(tppz)(H2O)]and [Mn(N3)(NO3)(tppz)(H2O)], have beentested as catalysts in oxidation of alcohol toaldehydes/ketones using oxone (2KHSO5ÆKHSO4ÆK2SO4) as an oxidant under biphasicreaction conditions (CH2Cl2/H2O) and tet-ra-n-butylammonium bromide as phasetransfer agent under air at room tempera-ture and as catalysts in oxidation of sulfidesto sulfoxides with UHP (urea hydrogenperoxide) as oxidant.

viii Contents

Pei-Hua Zhao, Ya-Qing Liu andGui-Zhe Zhao


Synthesis, characterization and crystal struc-tures of carboxy-functionalized diiron propane-dithiolate complexes

Reactions of the known complex A withClCH2CH2OH or p-IC6H4OH in the presenceof DMAP and DCC gave the carboxy-functionalized all-carbonyl complex 1 or2, respectively. Further treatment of 1 withPPh3 in the presence of Me3NOÆ2H2Oafforded the PPh3-monosubstitued com-plex 3, together with the PPh3-disubstituedcomplex 4. The new complexes 1–4 werecharacterized by combustion analysis, IRand NMR spectroscopies, as well as bysingle crystal X-ray diffraction analysis.

Gerald I. Spijksma,Gulaim A. Seisenbaeva,Henny J.M. Bouwmeester,Dave H.A. Blank and Vadim G. Kessler


Zirconium and hafnium tert-butoxides and tert-butoxo-b-diketonate complexes – Isolation,structural characterization and application inthe one-step synthesis of 3D metal oxidenanostructures

The paper reports structure and reactivityfor tert-butoxide complexes of Zr(IV) andHf(IV) in the solid state and solution.Thermal decomposition of Zr3O(OtBu)10

produces spontaneously the hedgehog typenanostructures.

Luca Rigamonti, Stefano Carlino,Yassin Halibi, Francesco Demartin,Carlo Castellano, Alessandro Ponti,Roberta Pievo and Alessandro Pasini


Copper 1D coordination polymers and dimers:Role of the carboxylate and the ammoniumcation, crystal structures and magnetic studies

Reaction of copper carboxylates with car-boxylic acids and amines gave two new 1Dcoordination polymers [Cu2(syn,syn-g1:g1:l-RCOO)4(anti,anti-g1:g1:l-RCOO)(Et3NH)]n

with R = Me (1) and H (2), and two newdimers [Cu2(syn,syn-g1:g1:l-RCOO)4(anti-g1-RCOO)2(ammonium)2] with R = Ph,ammonium = Et3NH+ (3) and R = Me, am-monium = Et2NH2

+ (4); compound 1 showsa strong antiferromagnetic coupling withinthe dimer (2J1 = )310.8(1) cm)1) and aweak antiferromagnetic coupling betweennearest dimers (2J2 = )25(1) cm)1).

Min Young Hyun, In Hong Hwang,Myoung Mi Lee, Hyun Kim,Kyung Beom Kim, Cheal Kim,Ha-Yeong Kim, Youngmee Kim andSung-Jin Kim


ZnII coordination polymers constructed withmalonate and bipyridyl ligands: Photolumines-cence and heterogeneous catalytic reactivity

Four three-dimensional ZnII frameworkswith the general formula [{Zn(H2O)(l-mal-onate)}2(l-bipyridyl)], containing water oracetonitrile solvates, have been prepared,and their luminescence properties andheterogeneous catalytic reactivities arediscussed.

ixContents

Grzegorz Romanowski and Jaromir Kira


Oxidovanadium(V) complexes with chiraltridentate Schiff bases derived from R())-phe-nylglycinol: Synthesis, spectroscopic character-ization and catalytic activity in the oxidation ofsulfides and styrene

A series of vanadium(V) complexes withchiral tridentate Schiff base ligands, ob-tained by the single condensation of R())-phenylglycinol with carbonyl compounds,were prepared and characterized. Thevanadium(V) complexes have the abilityto catalyze the oxidation of sulfides [PhSR(R = Me, Bz)] in good yields and enantio-meric excesses. These complexes are alsocatalytically active in the oxidation ofstyrene to styrene oxide, benzaldehyde,benzoic acid, phenylacetaldehyde and1-phenylethane-1,2-diol.

O

N O

R3

R2

R4

R1

O-V=O(L)O

V

Hassan Hadadzadeh, Mona Salimi,Matthias Weil,Mohammad Taghi Behnamfar andFarivash Darabi


Complex conversion of the redox pair CoIII–NO2

to CoII–NO3: Synthesis, crystal structure andDNA-binding of trans,trans,trans-[Co(py)2

(H2O)2(NO3)2]

The mononuclear Co(II) complex trans,-trans,trans-[Co(py)2(H2O)2(NO3)2] has beenprepared under atmospheric conditions viaa redox reaction of the starting materialNa3[Co(NO2)6]. The interaction of the com-plex with FS-DNA has been investigated byelectronic absorption, competitive fluores-cence titration, circular dichroism andvoltammetric techniques.

Marvadeen A. Singh-Wilmot,Rochette A. Sinclair, Michael Andrews,Claire Rowland, Christopher L. Cahill andMuralee Murugesu


Nonanuclear lanthanide(III) nanoclusters:Structure, luminescence and magnetic proper-ties

A series of nonanuclear lanthanide(III)nanoclusters was successfully synthesizedfrom (2-hydroxy-5-methylphenyl)propan-1-one, and characterized by photolumines-cence, magnetic susceptibility and X-raycrystallography.

CH3

OH

C H3

O

+ Ln(ClO4)3. 6H2O+ Et3N MeOH

Papia Datta, Dibakar Sardar, Rajat Saha,Tapan Kumar Mondal andChittaranjan Sinha


Structure, photophysics, electrochemistry andDFT calculations of [RuH(CO)(PPh3)2(coumari-nyl-azo-imidazole)]

[RuH(CO)(PPh3)2(coumarinyl-N@N-imida-zole)]0/+ complexes have been spectrosco-pically characterized and confirmed byX-ray structure determination. The cyclicvoltammetry shows Ru(III)/Ru(II) andRu(IV)/Ru(III) redox couples along withazoimine reduction. They are emissive atroom temperature. Theoretical calculationsexplain the electronic structure, spectraland redox properties of the complexes.

x Contents

Jessica R. Lamb, Valeria A. Stepanova andIrina P. Smoliakova


Transcyclopalladation on silica gel

The use of silica gel as a ‘‘green’’ mediuminstead of solvents in transcyclopalladationof BnSMe, BnSPh, BnPPh2, 8-methylquino-line and 1,3-bis(methylthiomethyl)ben-zene with acetato- and chloro-bridgeddimeric cyclopalladated complexes derivedfrom N,N-dimethylbenzylamine providedthe corresponding C,S-, C,N-, C,P- andC,S,C-palladacycles in 39–65% yield.

En-Cui Yang, Xi-Ying Zhang,Xiu-Guang Wang, Zhong-Yi Liu andXiao-Jun Zhao


Four manganese(II) 3-amino-1,2,4-triazolecomplexes incorporated with different polycar-boxylate coligands: Synthesis, structures andmagnetism

Four 3-amino-1,2,4-triazole (atz)-basedmagnetic complexes, two 4-connectedCdSO4-type frameworks, a discrete trinuc-lear entity, and a layered motif, wereobtained, exhibiting weak antiferromag-netic interactions transmitted by l-syn,anti-COO) and/or l-N2,N4-atz mediatorsin the nearest neighbours of the local bi-and trinuclear magnetic subunits.

Paulina Tsiliki, Franc Perdih, Iztok Tureland George Psomas


Structure, DNA- and albumin-binding of themanganese(II) complex with the non-steroidalantiinflammatory drug niflumic acid

The mononuclear manganese(II) complexof the non-steroidal antiinflammatory drugniflumic acid [Mn(O-niflumato)2(metha-nol)4] exhibits enhanced binding behaviourtowards DNA and serum albumins than thefree drug.

Mojtaba Bagherzadeh, Maryam Zare,Vahid Amani, Arkady Ellern andL. Keith Woo


Dioxo and oxo-peroxo molybdenum(VI) com-plexes bearing salicylidene 2-picoloyl hydra-zone: Structures and catalytic performances

MoO2(sal-phz)(CH3OH) and MoO(O2)(sal-phz)(CH3OH) have been synthesized andstudied as catalysts for the epoxidation ofolefins. The MoO2(sal-phz)(CH3OH) com-plex exhibits high catalytic activity for theepoxidation of olefins, whereas the peroxoanalogue is inert to the reaction. The lack ofreactivity of the peroxo complex rules outthe peroxo species as the intermediateresponsible for oxygen transfer in thereaction pathway.

xiContents

Ramalingam Thirumoorthi andTristram Chivers


Structure of the telluroketone TeC(PPh2N-SiMe3)2 coordinated to an Li8O6 cluster

The title compound is obtained as acentrosymmetric dimer comprised of twomolecules of the telluroketone TeC(PPh2N-SiMe3)2 which are N,Te,N-coordinated totwo LiOLi units of the neutral dimeric Li8O6

cluster [Li8(l5-O)2(l5-OH)4(C4H8O)4].

Saugata Konar, Atanu Jana, Kinsuk Das,Anamika Dhara, Sudipta Chatterjee,Luca M. Carrella, Eva Rentschler andSusanta Kumar Kar


An intramolecular antiferromagneticallycoupled pentanuclear homoleptic Mn(II) clus-ter: Synthesis, crystal structure, spectral andmagnetic property

Synthesis, crystal structure, spectral andmagnetic behavior of a homoleptic penta-nuclear Mn5 (II) cluster derived from aditopic ligand (5(E)-5-methyl-N¢-(pyridin-2-ylmethylene)-1H-pyrazole-3-carbohydra-zide), PzOPyH.

Kristen M. Roberts, Morgan A. Flahiveand James E. House


Thermodynamics of dissolution of ferrocene inn-octane, methanol, and acetonitrile

The solubility of ferrocene in n-octane,methanol, and acetonitrile has been stu-died to determine the thermodynamicquantities for dissolution. As expected fora nonpolar organometallic compound, so-lubility is greatest in n-octane. Entropychanges are discussed in terms of order inthe solvents and solvation of ferrocenemolecules.

Fe

-3.4

-3.2

-3.0

-2.8

-2.6

-2.4

-2.2

-2.0

-1.8

-1.6

-1.40.0032 0.0033 0.0034 0.0035 0.0036 0.0037

1/T, K-1

ln (s

olub

ility,

M)

n-OctaneAcetonitrileMethanol

Yong-Bin Lai, Chen-Shiang Lee,Wan-Jung Lin, Abbas Raja Naziruddinand Wen-Shu Hwang


Bis-chelate N-heterocyclic tetracarbene Ru(II)complexes: Synthesis, structure, and catalyticactivity toward transfer hydrogenation of ke-tones

Ru(II) complexes with two chelating di-N-heterocyclic carbenes (NHC) and two acet-onitrile ligands were synthesized andstructurally characterized. The complexesprove to be an efficient catalyst for transferhydrogenation of ketones.

0 10 20 30 40 50 600

20

40

60

80

100

conv

ersi

on (%

)

time (min)

1.0 mol% 0.10 mol% 0.010 mol%

xii Contents

Dasarath Mal, Rupam Sen, Paula Brandãoand Zhi Lin


Crystallization of five new supramolecular net-works with both bipyridyl and dicyanamideligands

Five new supramolecular networks havebeen crystallized with various structuresdepending highly on the experimentalconditions. The networks are ensured byintermolecular hydrogen bonding, andcontain both bpy and dca ligands. Onecompound contains water clusters, whilethe dca ligand is disordered in two com-pounds.

Susobhan Biswas, Rajat Saha,Ian M. Steele, Kamalendu Dey andSanjay Kumar


2D Ferromagnetic sheet of antiferromagnetictrimeric metal cores

Syn–syn and l-oxo bridging of acetateforms an antiferromagnetic trimeric metalcore and syn–anti and anti–anti bridging ofacetates among the trimeric units induce aferromagnetic interaction while the com-plex shows an overall ferromagnetic inter-action.

Bhaskar Biswas, Merry Mitra,Jaydeep Adhikary, G. Rama Krishna,Partha Pratim Bag, C. Malla Reddy,Nuria Aliaga-Alcalde,Tanmay Chattopadhyay, Debasis Das andRajarshi Ghosh


Synthesis, X-ray structural and magnetic char-acterizations, and epoxidation activity of a newbis(l-acetato)(l-alkoxo)dinuclear iron(III) com-plex

The synthesis, crystal structure and variabletemperature magnetic measurements of a new

dinuclear Fe(III) complex, [Fe2(l1,3-O2Cfn)(OH2)(MeOH)Cl2L] (1) [fn = furan, L = N,N¢-bis(salicyal-dehydene)-1,3-diaminopropan-2-ol], is reported.From X-ray diffractometry, it was shown thateach Fe(III) centre in 1 is in a distorted octahedralenvironment. A variable temperature magneticstudy reveals strong antiferromagnetic behaviourof 1 with J = )22.2 ± 0.1 cm)1. Use of 1 as analkene epoxidation catalyst towards (E)-stilbeneand styrene with tert-butyl hydrogen peroxide(TBHP) and iodosylbenzene (PhIO) reveals thatTBHP is the better oxidant in terms of the yield ofthe reaction.

Fe

OOC

O

Fe

NO

OO

NHC CH

OH2

Cl

Cl

OCH3H

HFe complex

Oxidant, Solvent

O

H Ph

PhH

Ph

Ph

H

Somnath Roy, Ray J. Butcher,Mohamed Salah El Fallah, Javier Terceroand João Costa Pessoa


An unusual half-open cubane-like tetranuclearcopper(II) complex supported by both l-alkoxoand l3-hydroxo bridges: Structure, magneticproperties, EPR and DFT studies

The polydentate compound H-PHMPreacts with Cu2+ to yield a tetranuclearCu-complex with a [Cu4(l-O)2(l3-OH)2]half-open cubane core. A variable tempera-ture magnetic study indicates the existenceof antiferromagnetic interactions (J1 =)304.0 cm)1 and J2 = )127.3 cm)1), thisbeing corroborated by DFT calculations.

xiiiContents

Adedayo Fashina, Edith Antunes andTebello Nyokong


Characterization and photophysical behavior ofphthalocyanines when grafted onto silica nano-particles

Silica nanoparticles are functionalized withzinc phthalocyanine complexes containinga free carboxyl group which facilitates thecovalent attachment of the phthalocya-nines on the silica surface via amide bondformation. The phthalocyanine functiona-lized silica nanoparticles showed higherfluorescence and triplet quantum yields aswell as longer triplet lifetimes compared tothe free phthalocyanine.

N

N

N

N

N

N NN

Zn

R

R

R

R

R=

COOH

DMF 24h

+O

O

Si

OEt

H2N

O

O

O

Si

OEt

HN

O

N

N

N

N

N

N NN

Zn

COOH

O

HOOCCOOH

O

O

O

Parvej Alam, Inamur Rahaman Laskar,Clàudia Climent, David Casanova,Pere Alemany, Maheswararao Karanam,Angshuman Roy Choudhury andJ. Raymond Butcher


Microwave-assisted facile and expeditivesyntheses of phosphorescent cyclometallatediridium(III) complexes

The microwave mediated syntheses of aseries of cyclometallated heteroleptic com-plexes of iridium(III) have been carried outand the time taken via this technique hasbeen shown to be much shorter as com-pared to conventional routes. Thesesynthesized complexes mostly emit lightthroughout the visible range. Complexeshaving phosphorous coordinating ancillaryligands showed blue-shifted emissions ascompared to (O^O), (O^N) and (N^N)coordinating ligands.

Michael K. Ainooson, Ilia A. Guzei,Lara C. Spencer and James Darkwa


Pyrazolylimine iron and cobalt, and pyrazo-lylamine nickel complexes: Synthesis andevaluation of nickel complexes as ethyleneoligomerization catalysts

A series of pyrazolylimine iron and cobalt,and pyrazolylamine nickel complexes havebeen synthesized and characterized. Thenickel complexes are excellent catalysts forethylene conversion to butenes and hex-enes.

Butenes + Hexenes(i) EtAlCl2(ii) Toluene

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