prelims, contents pages

Contents

G.E. Buono-Core, A.H. Klahn, G. Cabello andL. Lillo

Polyhedron 62 (2013) 1

Characterization of amorphous Pt/ZnO filmsgrown on silicon(1 0 0) substrates by aphotochemical metal organic deposition andtheir potential use as gas sensors

Pt loaded zinc oxide thin films have beensuccessfully prepared by direct UV irradia-tion of amorphous films of b-diketonatecomplexes on Si(1 0 0) substrates. Photode-posited films were characterized by X-rayphotoelectron spectroscopy (XPS) and atom-ic force microscopy (AFM). Sensing capaci-ties of the Pt/ZnO films towards carbonmonoxide were evaluated.

Ildikó Turi, Daniele Sanna,Eugenio Garribba, Giuseppe Pappalardoand Imre Sóvágó


The effect of non-coordinating side chains onthe metal binding affinities of peptides ofhistidine

The octapeptide Ac-GTHSMKHM-NH2

selectively binds copper(II) and nickel(II)ions. The -GTH- sequence is preferred fornickel(II) binding, while -MKH- favourscoordination of copper(II) ions.

2

-

-

2

3

-

2

-

-

-Ni2+

2+Cu

Maryam Khosravi M., Merritt B. Andrus,Scott R. Burt and Brian F. Woodfield


Generalized preparation method andcharacterization of aluminum isopropoxide,aluminum phenoxide, and aluminum n-hexyl-oxide

Aluminum, alcohol and HgCl2 have beenemployed in the synthesis of aluminumn-hexyloxide (AH), aluminum phenoxide(APh) and aluminum isopropoxide (AIP)with high yields and purity.

OAlAl + 3 n-Hexyl-OH

Al + 3Ph-OH

OAl

Al +3 i-PrOH Al O

+ 3/2H2

+ 3/2H2

+ 3/2H2

HgCl2 (0.001 mol)

HgCl2 (0.001 mol)

HgCl2 (0.001 mol)

3

3

3

Elsevier Ltd.

Polyhedron 62, 7 October 2013

Contents lists available at SciVerse ScienceDirect

Polyhedron

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

Sengottaiyan Poornima,Sellamuthu Anbu,Rajendran Ravishankaran,Shanmugam Sundaramoorthy,K. Natesan Vennila, Anjali A. Karande,Devadasan Velmurugan andMuthusamy Kandaswamy


DNA and protein targeting 1,2,4-triazole basedwater soluble dinickel(II) complexes enhancesantiproliferation and lactate dehydrogenaseinhibition

A new class of water soluble triazole baseddinickel(II) complexes have been synthe-sized and evaluated their DNA, proteinbinding, cleavage and anticancer proper-ties.

Sen-ichi Aizawa, Koichi Fukumoto andTatsuya Kawamoto


Effect of phosphine and phosphine sulfideligands on the cobalt-catalyzed reductive cou-pling of 2-iodobutane with n-butyl acrylate

Steric and electronic effects of phosphineand phosphine sulfide ligands on thecobalt-catalyzed reductive coupling of analkyl halide, 2-iodobutane, with an acti-vated alkene, n-butyl acrylate, are re-ported. The observed differences in thecatalytic activity provide insight into thereaction mechanism of the catalytic cycleand knowledge for choosing the ligand ofthe cobalt catalyst.

O

O-n-BuO-n-Bu

OCo(II)L or L2 0.04 mmol

Zn, H2O / CH3CN, 353 KI +

P

PS S S

PP

S

P PP P P

P

PS S

PP

P

PP

P

P PO O

L =

Franco Cataldo and Vlado Kanazirev


Synthesis and thermal stability of mercurydiacetylide Hg(CBCH)2

Mercury diacetylide was synthesized and studied byFT-IR spectroscopy, both in the mid and far infrared,and electronic absorption spectroscopy. The spectraldata are consistent with the structure H–CBC–Hg–CBC–H. Mercury diacetylide is insoluble in commonsolvents but shows a minimal solubility in ethanoland tetradecane. The thermal stability of mercurydiacetylide was studied by thermogravimetry (TGA),differential thermal analysis (DTA) and differentialscanning calorimetry (DSC). In an open crucible under

nitrogen, mercury diacetylide undergoes an exother-mal and explosive decomposition releasing 725.6 J/gwith an onset temperature of about 250 �C and a peaktemperature of 287 �C. The decomposition occurs at ahigher temperature in a sealed crucible (onset 326 �Cand peak 337 �C). Using the TGA–FT-IR analyticaltechnique it has been found that the deflagration ofmercury diacetylide produces elemental carbon,elemental mercury and acetylene. The enthalpy offormation of mercury diacetylide has been deter-mined for the first time. The explosive parameters ofmercury diacetylide have been compared with thoseof other common explosives showing that it is adangerous and powerful explosive.

Atanu Jana, Saugata Konar, Kinsuk Das,Sangita Ray, James A. Golen,Arnold L. Rheingold,Mohamed Salah El Fallah,Sanghamitra Mukherjee, Samik Gupta,Armando J.L. Pombeiro andSusanta Kumar Kar


A [2 · 2] Cu4 molecular grid and a Mn5 clusterderived from a 1-(2-pyridyl)pyrazole basedpolytopic ligand – Synthesis, structure, mag-netic properties and catalytic activity in theallylic oxidation of cyclohexene

The homoleptic [2 · 2] tetranuclear com-pound [Cu4(PyPzCAP)4](NO3)4Æ8H2O (1)and the pentanuclear Mn(II) cluster[Mn5(PyPzCAP)6](ClO4)4Æ4C6H6 (2) areself-assembled from the ditopic pro-ligandHPyPzCAP. Complex 1 shows a ferromag-netic exchange interaction (J = +4.62 cm)1

and g = 2.05), whereas 2 shows a weakantiferromagnetic interaction (J = )2.73cm)1 and g = 2.02). Both complexes 1 and2 catalyze the allylic oxidation of cyclohex-ene to cyclohex-2-ene-1-one with goodselectivity and an excellent overall turn-over number.

vContents

Kazem Barati,Mohammad Hossein Habibi,Morteza Montazerozohori,Hooshang Shafieyan, Ross W. Harringtonand William Clegg


Synthesis, crystal structure and photo-inducedisomerization of [N,N¢-bis(4-fluorobenzylidene)-ethylenediamine]bromo(triphenylphosphine)-copper(I)

The distorted-tetrahedral title complex isobtained as an EE isomer, but is convertedto the ZZ form on visible irradiation, forwhich the rate constant and quantum yieldhave been determined.

Manuel A. Escobar, Danilo H. Jara,Ricardo A. Tapia, Luis Lemus,Roland Fröhlich, Juan Guerrero andRené S. Rojas


Copper(I) complexes bases on a newindazol-4,7-dione ligand

The synthesis of two new isomeric ligands,1-(1-((2,6-diisopropylphenyl)imino)ethyl)-1H-benzo[f]indazole-4,9-dione (La) and2-(1-((2,6-diisopropylphenyl)imino)ethyl)-2H-benzo[f]indazole-4,9-dione (Lb), and oftheir [Cu(I)(Lb)2] (ClO4) (1) homoleptic and[Cu(I)(Lb(PPh3)2] (ClO4) (2) heterolepticcopper(I) complex derivatives is reported.The chemical stability, and the spectro-scopic and electrochemical properties ofthe complexes are discussed.

Deividi A. Cavarzan, FranciscoD. Fagundes, Otávio Fuganti,Caroline W.P. da Silva, CarlosBasílio Pinheiro, Davi F. Back,Andersson Barison, André L. Bogado andMárcio P. de Araujo


Mixed phosphine/diimines and/or aminesruthenium carbonyl complexes: Synthesis,characterization and transfer-hydrogenation

Complexes with the general formula trans-[RuCl2-(CO)(PR3)(N–N)] (N–N = diimines and/or amines;PR3 = triphenylphosphine or tri-p-tolylphosphine)

were synthesized by reacting trans-[RuCl2(CO)-(dmf)(PR3)2] (dmf = N,N-dimethylformamide) andthe appropriate N–N donor ligands and the com-plexes were tested as pre-catalyst for the reductionof acetophenone in transfer-hydrogenation condi-tions, using isopropanol as the hydrogen source. Thecatalyst/base/substrate molar proportion of1:20:1000 yielded conversions up to 83% in 24 h,whereas the proportion 1:20:500 furnished conver-sions up to 96% in 4 h. The complexes containing theligands ampy and en were the most active – the‘‘RuH-NH’’ unit promoted reactions via the outer-sphere mechanism.

Zdenek Spichal, Andrej Jancarik,Ctibor Mazal, Jiri Pinkas, Pavla Pekarkovaand Marek Necas


Lanthanide coordination polymers with bis(di-phenylphosphoryl)bicyclo[1.1.1]pentane

The reaction of 1,3-bis(diphenylphosphor-yl)bicyclo[1.1.1]pentane (1) with lantha-nide nitrates provided a series of layerednetwork coordination polymers Ln(1)1.5-(NO3)3 (Ln = Ce, Pr, Nd, Eu, Tb, Er, Yb, Lu).Crystal structures of all members of theseries were determined by single crystalX-ray diffraction and were found isostruc-tural. The compounds were studied by IRspectroscopy, luminescence spectroscopy,thermal analysis (TG/DSC) and powderX-ray diffraction (PXRD) techniques.

vi Contents

N.C. Yumata, G. Habarurema, J. Mukiza,T.I.A. Gerber, E. Hosten, F. Taherkhaniand M. Nahali


Rhenium complexes of di-2-pyridyl ketone, 2-benzoylpyridine and 2-hydroxybenzophenone:A structural and theoretical study

The reactions of di-2-pyridyl ketone (dpk),2-benzoylpyridine (zpy) and 2-hydroxy-benzophenone (Hbp) with [Re(CO)5Cl] andtrans-[ReOX3(PPh3)2] (X = Cl, Br) led to theisolation of the complexes fac-[Re(CO)3(dp-kÆOCH3)], cis-[ReOBr2(dpkÆOH)]Æ2(dpkH+Br)),[ReIIIX3(zpy)(PPh3)], fac-[Re(CO)3(zpy)Cl],cis-[ReOX2(bp)(PPh3)] and cis-[ReIIIBr2(bp)-(PPh3)2].

Isabela L. Paiva, Gustavo S.G. de Carvalho,Adilson D. da Silva, Pedro P. Corbi,Fernando R.G. Bergamini,André L.B. Formiga, Renata Diniz,Weberton R. do Carmo, Clarice Q.F. Leite,Fernando R. Pavan and Alexandre Cuin


Silver(I) complexes with symmetrical Schiffbases: Synthesis, structural characterization,DFT studies and antimycobacterial assays

Two new silver(I) complexes of two Schiffbases were synthesized. Antimycobacterialstudies were evaluated and the silvercomplexes showed high activity againstMycobacterium tuberculosis, reporting amore potent activity action than commer-cial Silver Sulfadiazine compound. Fullcharacterization was performed to twocomplexes.

Mousa Al-Noaimi, Ismail Warad,Obadah S. Abdel-Rahman, FirasF. Awwadi,Salim F. Haddad and Taibi B. Hadda


Synthesis, structure, spectroscopic properties,electrochemistry, and DFT correlative studies oftrans-[Ru(P-P)2Cl2] complexes

Five trans-[Ru(P-P)2Cl2] complexes were prepared byreacting RuCl2(PPh3)3 with P-P ligands {P-P =(hdppp) = 3-hexyl-1,3-bis(diphenylphosphino)propane(1); (dppp) = 1,3-bis(diphenylphosphino)propane (2);(dppe) = 1,2-bis(diphenylphosphino)- ethane (3)(dppe); (dppm) 1.1¢-bis(diphenylphosphino)methane

(4); 1,2-bis(diphenylphosphino)ethylene (5)}. Thecomplexes were characterized by elemental analysis,IR, 1H, 13C and 31P{1H}NMR, FAB-MS and TG/DTA.These Ru(II) complexes showed Ru(III)/Ru(II) quasir-eversible redox couple. The molecular structures of thecomplexes 1 and 3 were determined by X-ray crystal-lography, and their spectroscopic properties werestudied. The two complexes adopt a distorted transoctahedral coordination and ruthenium(II) ions arelocated on a crystallographic centre of symmetry.Based on the optimized structures, computationalinvestigations were carried out in order to determinethe electronic structures of the complexes. Theelectronic spectra of 1 and 1+ in dichloromethanewere calculated with the use of time-dependent DFTmethods, and the electronic spectra of the transitionswere correlated with the molecular orbitals of thecomplexes.

Altug Mert Sevim,H. Yasemin Yenilmez and ZehraAltuntas Bayır


Synthesis and photophysical properties of novel(trifluoromethyl)phenylethynyl-substitutedmetallophthalocyanines

The synthesis of symmetrically substituted novelmetallophthalocyanines (M = Zn(II), Cu(II), Co(II))bearing four 3,5-bis(trifluoromethyl)phenylethynylmoieties was achieved by following the well-knownpalladium-catalyzed cross-coupling methodology.The structures of the newly synthesized molecules

were characterized by using various spectroscopictechniques. The aggregative properties of the novelcompounds were investigated in different concentra-tions. General trends were described for fluorescencequantum yield and lifetime of novel zinc derivativein tetrahydrofuran. The fluorescence of the complexis quenched by 1,4-benzoquinone (BQ), and fluores-cence quenching properties have been investigated.

viiContents

Bárbara Tirloni, Ernesto Schulz Lang andGelson Manzoni de Oliveira


Synthesis, crystal structure and optical featuresof new Hg–Se clusters

Hg(SePh)2 reacts with HgI2/2,2¢-bipyridine,HgI2/1,10-phenantroline, HgI2/triphenyl-phosphine and HgBr2/2,2¢-bipyridine togive the respective clusters [Hg4I4(-SePh)4(2,2-bipy)2]Æ2dmf (Ph = phenyl;dmf = dimethylformamide), [Hg4I2(-SePh)6(phen)2], [Hg8I2Se(SePh)12(dmf)2](3) and [Hg8Br5Se(SePh)9(2,2-bipy)2] (4).The bulky nanoclusters 3 and 4 differmainly with respect to the existence ofterminal and bridging bromide ions in 4.The optical band gaps of the title com-pounds were determined by measuringtheir UV–Vis diffuse reflectance spectra.

Damir A. Safin, Maria G. Babashkina,Michael Bolte and Yann Garcia


Novel facile single source precursor N-phos-phorylated bis-thiourea [NHC(S)NHP(O)-(OPh)2]2 for the ‘‘criss-cross’’ formation ofs-triazolidino[1,2-a]-s-triazolidine-3,7-dithiones:First structurally characterized representative

Reaction of hydrazine with S@C@N–P(O)(OPh)2 leads to new bis-thiourea[NHC(S)NHP(O)(OPh)2]2, which was foundto be a facile single source precursor for theformation of s-triazolidino[1,2-a]-s-triazo-lidine-3,7-dithiones by the reaction withketones.

Muhammad Altaf, Helen Stoeckli-Evans,Alexandre Cuin, Daisy Nakamura Sato,Fernando Rogério Pavan,Clarice Queico Fujimura Leite,Saeed Ahmad, Mohammed Bouakka,Mostafa Mimouni, Fatima Zahra Khardliand Taibi Ben Hadda


Synthesis, crystal structures, antimicrobial,antifungal and antituberculosis activities ofmixed ligand silver(I) complexes

Silver(I) mixed ligand mononuclear andbinuclear bridging complexes have showninteresting anti-proliferative activityagainst different strains of Gram+ andGram) bacteria, one strain of fungous aswell as Mycrobaterium tuberculosis H37Rv.

John Novales, Nicolette Jonkhoff andJ. Henry Acquaye


Synthesis, characterization and X-ray crystalstructures of ruthenium polypyridyl and2-(2¢-hydroxyphenyl)-benzoxazole complexes:Reactivity with 1-methylimidazole, purine,glutathione and CT-DNA

A number of ruthenium terpyridine com-plexes incorporating the bidentate ligand2-(hydroxyphenyl)-benzoxazole have beensynthesized and characterized. The crystalstructures of three of the complexes havebeen determined. The reactivity of theaqua complexes with 1-methylimidazole,glutathione, purine and CT-DNA have beenstudied.

viii Contents

B. Machura, A. Switlicka-Olszewska,R. Kruszynski, T. Gron, M. Oboz andH. Duda


Synthesis, structural and magnetic character-ization of oxalate copper(II) complexes ofphthalazine, 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine and 6,7-dimethyl-2,3-di(2-pyridyl)qui-noxaline. Supramolecular architectures stabi-lized by hydrogen bonding

The paper presents a combined experimental andcomputational study for three oxalate copper(II) com-plexes [Cu(ptz)2(C2O4)(H2O)]Æ1.5H2O (1), [Cu(dppt)-

(C2O4)(H2O)]ÆH2OÆMeOH (2) and [Cu(dmdpq)(C2O4)-(H2O)]Æ5H2O (3) (ptz = phthalazine, dppt = 3-(2-pyri-dyl)-5,6-diphenyl-1,2,4-triazine and dmdpq = 6,7-di-methyl-2,3-di(2-pyridyl)quinoxaline). The compoundshave been studied by IR, UV–Vis spectroscopy andsingle crystal X-ray analysis. Due to the presence ofcoordinated water molecules and oxalate groupstogether with the lattice solvent molecules (water andmethanol) their crystal structures are dominated by thehydrogen-bonding interactions that give rise to thesupramolecular architectures. The electronic spectra ofthe complexes [Cu(ptz)2(C2O4)(rH2O)], [Cu(dppt)(-C2O4)(H2O)] and [Cu(dmdpq)(C2O4)(H2O)] were ana-lyzed and the absorptions bands were assigned throughthe DFT/TDDFT procedures. Magnetic studies of allcomplexes under study showed paramagnetic behaviorwith large orbital magnetic contribution.

Chinduluri Sravani, Sadhana Venkatesh,Akella Sivaramakrishna,Kari Vijayakrishna, Hadley S. Clayton,John R. Moss, Viktor Moberg and Hong Su


Facile synthesis of platinum based heterobime-tallic carbonyl clusters from bis(1-alkenyl)Pt(II)precursors

A new route for the high yield synthesis of platinumcontaining mixed bimetallic carbonyl clusters of thetype [PtRu2(CO)8L2] (where L2 = dppe, 1,2-bis(diphe-nylphosphino)ethane or dppp, 1,3-bis(diphenylpho-sphino)propane; L = PPh3) by the reaction of

platinum-alkenyl [PtL2(1-alkenyl)2] precursors with[Ru3(CO)12] is reported. An unexpected multinuclearmixed cluster, [PtRu4(CO)13(l4-PCH2CH2CH2PPh2)],obtained under prolonged refluxing conditions wasalso isolated. All the products were isolated andcharacterized by various spectroscopic and analyticaltechniques. In solution, the complex [PtRu2(-CO)8(PPh3)2] gives [Pt2Ru(l-CO)3(CO)2(PPh3)3] andRu3(CO)11(PPh3). The structures and relative energiesof intermediates and transition states in the pro-posed reaction mechanism for the {PtRu2} clustershave been investigated using density functionaltheory.

Pt

L

LRu3(CO)12 Pt

L

L

Ru(CO)4

Ru(CO)4

1, n = 2L2 = dppp; dppe; dppmL = PPh3.

, 80oC, 8 hToluene

n

n

+

L = PPh3

L2 = dppm

RT

Pt

Ru

Pt

OC COPPh3

Ph3P PPh3

O

OO

Pt

Ru RuPh2P

Ph2P

Ph2P

PPh2

OCOC OCCO CO

O

Prasanta Kumar Bhaumik, Klaus Harmsand Shouvik Chattopadhyay


Counter anion modulated variation of denticityof NNO donor Schiff base in copper(II) com-plexes: Isolation of a zwitterionic Schiff base asthe metal complex

Three copper(II) complexes have beensynthesized and characterized. Complexes1 and 2 are monomeric. The asymmetricunit of complex 3 consists of two crystal-lographically different double end-on cya-nate bridged dimers containing squarepyramidal copper(II) centers. The denticityof the tridentate Schiff base has beenmodulated by the acidity of counter anions.The Schiff base in its zwitterionic form hasbeen isolated as the copper(II) complex.

Jan G. Małecki, Anna Maron, Iza Gryca,Asami Mori and Takayoshi Suzuki


Ruthenium(II) complexes with quinolinecarboxylate as a co-ligand

Ruthenium(II) complexes with the general formulas[Ru(H/Cl)(CO)(PPh3)2(L)] and cis/trans-[Ru(PPh3)2(L)2] (L = isoquinoline-1-carboxylate orquinoline-2-carboxylate) were synthesized and char-acterized by IR, 1H, 13C and 31P NMR, UV–Visspectroscopy and X-ray crystallography. The experi-mental studies were completed by quantum chemi-cal calculations, which were used to describe thenature of the interactions between the ligands and

the central ion, and the orbital compositions in thefrontier electronic structures. Based on a molecularorbital scheme, the calculated results allowed theinterpretation of the UV–Vis spectra obtained at anexperimental level. The luminescence properties ofthe complexes were determined.

ixContents

Guddekoppa S. Ananthnag,Namepalli Edukondalu, Joel T. Magueand Maravanji S. Balakrishna


Copper and palladium complexes of 2-(diphe-nylphosphino)-N,N-dimethylbenzylamine andits selenide derivative

The chalcogen derivatives and palladiu-m(II) and copper(I) complexes of 2-(diphe-nylphosphino)-N,N-dimethylbenzylamine,Ph2PC6H4CH2NMe2-o are described.

G. Soras, N. Psaroudakis, M.J. Manos,A.J. Tasiopoulos, D.G. Liakos andG.A. Mousdis


Synthesis, experimental and theoretical inves-tigation of a new type nickel dithiolene complex

A new nickel complex with an extended multisulfurdithiolene ligand, Ni(dmeodddt)2 (dmeodddt = 5,6-dimethoxy-5,6-dihydro-1,4-dithiine-2,3-dithiolate),has been synthesized. Its characterization was madeby electrochemical measurements, IR, UV–Vis, NMRand Raman spectroscopy. Its crystal structure wasresolved by X-ray diffraction on a single crystal.

Theoretical investigation was also performed and theresults were compared with the experimental find-ings. Through this comparison, we have gained aninsight into the properties of this new dithiolenecomplex.

Beata Cristóvão, Barbara Miroslaw andJulia Kłak


New mononuclear CuII and tetranuclear CuII2–

LaIII2 Schiff base complexes – Physicochemical

properties

The new compounds [CuL�(H2O)] (1) and [Cu2-

La2(L)2(NO3)6(EtOH)2] (2), derived from N,N¢-bis(5-bromo-3-methoxysalicylidene)propylene-1,3-dia-mine, were obtained and their physicochemicalproperties were investigated. In compound 1, theCu(II) ion occupies the inner N2O2 salen-type cavityof the Schiff base, whereas the water molecule is

encapsulated by O–H� � �O hydrogen bonds in thelarger O2O2 compartment of this ligand. In thebimetallic heterotetranuclear complex 2, the N2O2cavities of the organic ligand are also occupied byCu(II) ions, whereas La(III) ions are present in theO2O2 cavities. Moreover, the two symmetricallyindependent heterodinuclear fragments of this mo-lecule are bridged via nitrato ions linking the 3d and4f ions. The measurements of variable-temperaturemagnetic susceptibility as well the relationshipbetween the magnetization and magnetic fieldstrength in 1 and 2 revealed weak antiferromagneticinteractions between the CuII magnetic centers atlow temperature.

Poornima Singh, Ashok K.S. Chauhan,Ray J. Butcher and Andrew Duthie


Synthesis and structural aspects of 1-naphthyl-tellurium(IV) trichloride (1), bis(mesityl)tellur-ium(IV) dichloride (2) and bis(chlorobis(2-thiophenyl)tellurium)oxide (3)

Three tellurium(IV) derivatives 1-NplTeCl3

(1), Mes2TeCl2 (2) and (Tpn2TeCl)2O (3)have been synthesized and crystallogra-phically characterized. Preparation of 1 and2 involves oxidative addition of SO2Cl2 to1-Npl2Te2 and Mes2Te respectively. The 3has been obtained by the partial hydrolysisof Tpn2TeCl2. In 3, 1D supramolecular arraywas formed due to the intermolecularTe� � �Cl interactions.

x Contents

Sagarika Bhattacharya, Arpita Jana andSasankasekhar Mohanta


Syntheses, crystal structures and spectroscopyof di/tri/tetranuclear discrete and co-crystallinecopper(II)–NaI/ZnII/CdII complexes derived froma compartmental ligand: Inconsistency in theshifting of the copper(II) d–d band

This report presents the syntheses, crystalstructures, characterization and electronicspectroscopy of six heteronuclear copper(-II) complexes derived from the N,N¢-ethy-lenebis(3-methoxysalicylaldimine) ligand.Solid state electronic spectra of the com-pounds are correlated with the displace-ment of the copper(II) centers from thebasal N2O2 plane.

Z. Piskuła, M. Kubicki and S. Lis


The structural and spectroscopic studies ofUO2þ

2 complexes with diethyl benzylphospho-nate and diethyl (carboxymethyl)phosphonatein solution and in the solid state

Complexes of uranyl ion with diethylbenzylphosphonate (L1) and diethyl (car-boxymethyl)phosphonate (L2) ligands weresynthesized and characterized structurallyand spectroscopically. In the crystal struc-tures of the complexes [UO2(L1)2(NO3)2]and [UO2(L2)2(NO3)2] the uranyl groups arecoordinated in the equatorial plane by sixoxygen atoms, and the coordination poly-hedra of uranium ions are close to hex-agonal bipyramid, with uranyl oxygenatoms in apexes.

Sule Sahin Ün, Elif Özcan, Aylin Uslu,Fatma Yuksel and Adem Kılıç


Cyclotriphosphazene derivatives with threedifferent chiral centres: Synthesis, characteriza-tion and investigation of their stereogenicproperties

Cyclophosphazene derivatives with threedifferent stereogenic centres were synthe-sized and characterized. Also their stereo-genic properties were investigated by X-ray crystallography and CSA added 31PNMR spectroscopy.

Edwin C. Constable,Catherine E. Housecroft, Jonas Schönle,Srboljub Vujovic and Jennifer A. Zampese


Coordination polymers with 4¢-(4-(anthracen-9-yl)phenyl)- and 4¢-(4-(naphthalen-1-yl)phe-nyl)-4,2¢:6¢,400-terpyridines: Mono-, di- andheptazinc(II) nodes

Diversity in the assembly of coordinationpolymers in reactions of zinc(II) acetatewith 4¢-aryl-4,2¢:6¢,4 � �-terpyridine (aryl =4-(naphthalen-1-yl)phenyl or 4-(naphtha-

len-1-yl)phenyl): racemates or homochiralpolymers containing mononuclear{Zn(OAc)2} nodes, a one-dimensional poly-mer containing {Zn2(l-OAc)4}nodes, and aone-dimensional polymer with {Zn7(l-OAc)10(l4-O)2} cluster-nodes are described.

xiContents

Romana Ševcíková, Premysl Lubal,Maria Paula Cabral Campello andIsabel Santos


Kinetic study of formation/dissociation of Cu(II)and Zn(II) complexes of cyclen macrocyclicligand with pendant thiol group

The kinetic properties of copper(II) andzinc(II) complexes with cyclen-based li-gands having thiol pendant arms werestudied. The impact of thiol pendant armon kinetic and activation parameters of thecomplex formation/dissociation was inves-tigated.

Elena Fursova, Galina Romanenko andVictor Ovcharenko


Unpredictable polynuclear Ni(II) lactateformation

N(C4H9)4][NiPiv3] was synthesized, whosecomplex anion has only pivalate anions asligands that adopt a chelating coordination.The interaction of [N(C4H9)4][NiPiv3] withNi(II) salts in organic media led to theformation of a mixed-ligand hexanuclearcomplex, [Ni6L2(HL)2Piv6(HPiv)8], whereHPiv is pivalic acid, and L and HL are thelactic acid dianion and monoanion, respec-tively.

Antonio Sousa-Pedrares,María L. Durán-Carril, Jaime Romero,José A. García-Vázquez andAntonio Sousa


Synthesis and characterization of homolepticchromium(III) complexes containing pyridine-2-thionato ligands and of the co-crystal (1:1)bis(pyridine-2-thionato)(pyridine-2-dithionato)chromium(III) tris(pyridine-2-thionato) chro-mium(III)

Three homoleptic chromium(III) trischelatecomplexes [Cr(RpyS)3] (R = 3-Me3Si, 3-CF3

and 5-CF3) and a two-component co-crys-tal [Cr(pyS)3]/[Cr(pyS)2(pySS)] have beenprepared by the reaction of hexacarbonylchromium with the corresponding pyri-dine-2-thione ligand. The complexes werecharacterized by spectroscopy (IR, UV)methods and by X-ray crystallographictechniques.

Dursun Karaagaç, GünesSüheyla Kürkçüoglu, Okan Zafer Yesileland Murat Tas


Syntheses, thermal analyses, crystal structures,FT-IR and Raman spectra of 2D [Zn(NH3)2(l–ampy)M¢(l–CN)2(CN)2]n (M¢ = Ni(II), Pd(II) orPt(II)) complexes

The crystal structure of 1 reveals that theintramolecular C–H� � �N, intermolecular N–H� � �N hydrogen bonds and Ni(II)� � �p inter-actions link the polymeric chains into athree dimensional network. The experi-mental study on complex 1 has revealedthe great importance of the non-covalentNi(II)� � �p interactions between the Ni(II)ion and the 4-aminomethylpyridine ligand.

xii Contents

Roman V. Yizhak, Kateryna O. Znovjyak,Vladimir A. Ovchynnikov, TatianaYu. Sliva, Irina S. Konovalova, VolodymyrV. Medviediev, Oleg V. Shishkin andVladimir M. Amirkhanov


Synthesis and crystal structures of new diox-ouranium(VI) complexes based on carbacylami-dophosphates (CAPh). Investigation ofextraction properties of some CAPh ligands inrespect of dioxouranium(VI) nitrate

New coordination compounds of the for-mulae UO2(NO3)2(HL1)2, UO2(NO3)(L1)-(HL1) and UO2(L2)2(HL2), where HL1 =Cl3CCONHP(O)(N(CH2)5)2 and HL2 =Cl3CCONHP(O)(N(Et)2)2, were synthesizedand characterized by means of 1H NMR andIR spectroscopy and X-ray diffraction ana-lysis. The extraction of dioxouranium(VI)nitrate from HNO3 solutions using HL1,HL2 and HL3 (Cl3CCONHP(O)(N(CH2)4)2) intoluene was carried out.

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