Prelim v-xiv contents (synopsis and pictogram)

Volume 425, 30 January 2015

Contents lists available at ScienceDirect

Inorganica Chimica Acta journal homepage: www.elsevier.com/locate/ica

Contents Articles Sreedhar V. Kumar, Warrick K.C. Lo, Heather J.L. Brooks, James D. Crowley Inorganica Chimica Acta 425 (2015) 1 Synthesis, structure, stability and antimicrobial activity of a ruthenium(II) helicate derived from a bis-bidentate ‘‘click’’ pyridyl-1,2,3-triazole ligand

Taeko Kakizawa, Hisako Hashimoto, Hiromi Tobita Inorganica Chimica Acta 425 (2015) 7 Linking of phosphinidene-capped triruthenium carbonyl clusters with diphosphine ligands

Caihua Zhou, Yongning Liu, Xiang Zhao Inorganica Chimica Acta 425 (2015) 11 Effect of substituted sites and coordinated metal atoms on the absorption properties of porphyrin and phthalocyanine derivatives

Elsevier B.V.

A rare [Ru2L3]4+ ruthenium(II) triplystranded helicate was synthesized from a bis-bidentate ‘‘click’’ pyridyl-1,2,3-triazole ligand and RuCl3 in good yield (58%). This kinetically inert [Ru2L3]4+ system proved stable (over a period of days) when exposed to the common biological ligand histidine. The helicate displayed modest antibacterial activity against Staphylococcus aureus.

Two phosphinidene-capped triruthenium clusters were connected with diphosphines to afford large clusters. The reactions proceeded under hexane refluxing condition, and the desired products were obtained in high yields.

The electronic transition properties of eight porphyrin-based and phthalocyaninebased compounds are specially calculated by the density functional and its time dependent theory calculations. It is found that the substituted positions of the functional groups influence the NIR absorption properties of compounds. The relations between the absorption efficiency and the substituted positions of functional groups are revealed, and more efficient phthalocyanine-based dyes are designed.

vi

Yungen Ran, Jixing Xie, Yajuan Mu, Linfen Zhang, Bo Han Inorganica Chimica Acta 425 (2015) 17 A series of 2D Cd(II) coordination polymers constructed from dicarboxylate acids and a flexible imidazole-based ligand

Guang-Ning Liu, Wen-Juan Zhu, Ya-Nan Chu, Cuncheng Li Inorganica Chimica Acta 425 (2015) 28 Three d10 metal coordination compounds based on pyrazole-3-carboxylic acid showing mixed-ligand characteristic: Syntheses, crystal structures, and photoluminescent properties

Monika Mishra, Karishma Tiwari, Ashish Kumar Singh, Vinod P. Singh Inorganica Chimica Acta 425 (2015) 36 Versatile coordination behaviour of a multi-dentate Schiff base with manganese(II), copper(II) and zinc(II) ions and their corrosion inhibition study

Franz A. Mautner, Michael Scherzer, Christian Berger, Roland C. Fischer, Salah S. Massoud Inorganica Chimica Acta 425 (2015) 46 Synthesis, characterization and luminescence properties of zinc(II) complexes of pseudohalides and nitrite derived from 4azidopyridine

Contents

Five 2D Cd(II)-based coordination polymers have been obtained and characterized. Complexes 1 and 4 present binodal (3,4)-connected layers with 3,4L83 topology. Complexes 2 and 3 display 44-sql layers, of which 2 contains left- and righthanded helical chains. Complex 5 exhibits a sheet structure with hcb topology. Their thermal and luminescent properties were also investigated.

Reported here are the syntheses, structures and photoluminescence of three pyrazole3-carboxylic acid-based d10 metal coordination compounds with mixed-ligand characteristic. DFT calculations were performed to make clear their photoluminescence mechanisms.

Schiff base ligand, 2-amino-benzoic acid [1-(2-hydroxy-phenyl)-propylidene]-hydrazide shows versatile coordination behaviour and results the formation of mono-/ polynuclear complexes of Mn(II), Cu(II) and Zn(II). The corrosion-inhibition properties of the compounds have also been evaluated for mild steel in 1 M HCl medium.

The synthesis and characterization of four new zinc(II) complexes with 4-azidopyridine as co-ligand is reported. The azido complex 1 forms polymeric chains via diEO and di-EE azido bridges, whereas the complexes with NCS, NCO and NO2 form mono-nuclear species. The luminescence properties are also presented.

Contents

Wen-Li Zhang, Zhi-Peng Huang, Cheng-Jie Ma, Yu-Xia Zai, Qing Yang, Yun-Yin Niu Inorganica Chimica Acta 425 (2015) 52

vii

Five novel haloclusters possess 0–2D frameworks were prepared by the directing of cationic bolaamphiphiles template. The anion portion exhibit different configurations by varying the alkyl chain length.

dications

Novel bis(methylimidazolium) alkane bolaamphiphiles as templates for the construction of haloclusters supramolecules 1(2D)

Sunit K. Mal, Merry Mitra, Bhaskar Biswas, Gurpreet Kaur, Partha P. Bag, C. Malla Reddy, Angshuman Roy Choudhury, Nuria Aliaga-Alcalde, Rajarshi Ghosh Inorganica Chimica Acta 425 (2015) 61 Ligand template synthesis of an undecametallic iron(III) complex: X-ray structure, magnetism and catecholase activity An undecairon(III) oxo-hydroxo-carboxylato bridged aggregate [Fe11(l3-O)6(l3-OH)6(l-O2C-f)15] (1) has been synthesized and characterized by single crystal

Piyali Paul, Ray J. Butcher, Samaresh Bhattacharya Inorganica Chimica Acta 425 (2015) 67 Palladium complexes of 2-formylpyridine thiosemicarbazone and two related ligands: Synthesis, structure and, spectral and catalytic properties

Cibely S. Martin, Marcos F.S. Teixeira Inorganica Chimica Acta 425 (2015) 76 A comparison of charge-transfer mechanisms at rotated disk electrode for biomimetic binuclear and tetranuclear oxomanganese complex in aqueous solution

2(1D)

3(1D)

4(1D)

5(1D)

X-ray diffraction study. The anionic ligand N(2-hydroxyethyl)-3-methoxysalicylaldimine (L) has been used as template to synthesize such high nuclearity complex. Interestingly, the ligand neither enters into the coordination sphere nor crystallizes with the iron cluster. Bond distance data indicate that all the iron atoms in 1 are high-spin Fe(III) in Odonor environment. 1 behaves as an effective catalyst towards oxidation of 3,5-di-tert-butylcatechol in different solvents, viz. methanol, dichloromethane and acetonitrile, to its corresponding quinone derivative in aerial oxygen. The reaction follows Michaelis–Menten enzymatic reaction kinetics with turnover numbers (Kcat) 3.21 · 103, 1.23 · 103 and 1.11 · 103 h1 in methanol, dichloromethane and acetonitrile, respectively.

Reaction of 2-formylpyridine thiosemicarbazone and two related ligands (HL-R) with [Pd(PPh3)2Cl2] affords the mixedligand complexes 1–3 with a NNS-mode of binding from the thiosemicarbazones. These complexes have shown efficient catalytic efficiency towards C–C and C–N coupling reactions of different types.

The electrochemical and kinetic parameters were determined for two mimicking complexes ([Mn2IVO2(terpy)2(H2O)2]4+ and [Mn4IVO5(terpy)4(H2O)2]6+) by cyclic voltammetry and linear sweep voltammetry with rotating disk electrode (RDE).

+ PPh3

R = H, Me, Ph N

N N

R

NH2 N

H

Pd N

R

S N

S HL-R

NH2 1-3

viii

Jane E. Spenceley, William Henderson, Joseph R. Lane, Graham C. Saunders Inorganica Chimica Acta 425 (2015) 83 Isomerism in platinum(II) complexes of asymmetrically 1,3-disubstituted thiourea dianion ligands A series of thiourea dianion complexes [Pt{SC(NPh)NR}(PPh3)2] (R = Me, Et, Prn, Pri, Bun, But and p-tol) was synthesised from cis-[PtCl2(PPh3)2] and the asymmetrically disubstituted thioureas PhNHC(S) NHR in the presence of triethylamine base.

Kenta Imoto, Miho Takemura, Koji Nakabayashi, Yasuto Miyamoto, Keiko Komori-Orisaku, Shin-ichi Ohkoshi Inorganica Chimica Acta 425 (2015) 92 Syntheses, crystal structures, and magnetic properties of Mn–Nb and Co–Nb cyanidobridged bimetallic assemblies Cyanido-bridged Mn–Nb and Co–Nb bimetal assemblies, MnII2[NbIV(CN)8]Æ(L)2ÆnH2O (1: L = 5-aminopyrimidine, n = 5; 2: L = 5-methylpyrimidine, n = 4), and CoII2[NbIV(CN)8]Æ(4-pyri-

Pooja Bharati, A. Bharti, U.K. Chaudhari, M.K. Bharty, S. Kashyap, Udai P. Singh, N.K. Singh Inorganica Chimica Acta 425 (2015) 100 Trinuclear supramolecular Zn(II) complexes derived from N0 -(pyridine carbonyl) hydrazine carboperthioates: Synthesis, structural characterization, luminescent properties and metalloaromaticity

Jianxiang Wu, Wei Zhang, Aomin Tang, Yilong Gao, Yueyue Tan, Yong Men, Bohejin Tang Inorganica Chimica Acta 425 (2015) 108 A novel 2D supramolecular compound of zwitterion and polyoxoanion and its application in catalytic desulfurization

Contents

With the exception of the t-butyl complex, all complexes initially form the distal isomer, with the NR group remote from the platinum centre, and a coordinated NPh group; isomerisation occurs in solution to the thermodynamically more stable proximal isomer with a coordinated NR group. The isomerisation process was investigated by NMR spectroscopy and DFT calculations; the X-ray structure of the proximal isomer of [Pt{SC(=NPh)NEt} (PPh3)2] is also reported.

dinealdoxime)8Æ2H2O (3) are synthesized. 1 and 2 have isomorphic three-dimensional (3D) cyanido-bridged network composed of a square antiprism Nb sites, showing ferrimagnetism with Curie temperatures (TC) of 32 and 34 K, respectively, due to the antiferromagnetic coupling between MnII (S = 5/2) and NbIV (S = 1/2) through the CN groups. 3 has a 3D cyanidobridged network composed of a dodecahedral Nb site and axially distorted Co site, exhibiting ferromagnetism with a TC of 18 K. Magnetization versus rotation angle of single crystal reveals that 3 has a large coercive field of 15 000 Oe as crystal is oriented to a-axis, which is due to the strong magnetic anisotropy on distorted CoII.

Trinuclear complexes [Zn3(l-4-pchcp)2 (py)4] and [Zn3(l-3-pchcp)2(py)4] have been isolated containing N0 -(pyridine-3/4carbonyl) hydrazine carboperthioate which have been generated from potassium N0 (pyridine-3/4-carbonyl) hydrazine carbodithioates by in situ S–S coupling in the presence of pyridine. In complexes, the middle Zn(II) center has four coordinate tetrahedral arrangement bonded through two hydrazinic nitrogens and two sulfur atoms from two perthio ligands.

[C8H11N2O4]3PMo12O40Æ2CH3OHÆH2OÆin the P2(1)/ n space group of monoclinic system with a = 13. 1231(7), b = 26.5393(14), c = 20.0457(11) Å, a = 13.1231(7), V = 6833.7(6) Å3, C26H43Mo12N6O55P, Mr = 2501.91, Dcalc = 2.432 mg/m3, l = 2.262 mm1, F(0 0 0) = 4800, Z = 4, R1 = 0.0522 and wR2 = 0.1242. X-ray crystallography shows that, under catalysis of the polyoxometalate anion, one of the carboxyl groups in each zwitterionic molecule is esterified by methanol solvent. The polyoxometalate anions extend to a honeycomb-like inorganic layer via short contact interactions of O  O.

Ph3P

S Pt

Ph3P

R C

N

N Ph

Isomerisation Ph3P

S Pt

Ph3P

Ph C

N R

N

Contents

Marina Ya. Demakova, Dmitrii S. Bolotin, Nadezhda A. Bokach, Galina L. Starova, Vadim Yu. Kukushkin Inorganica Chimica Acta 425 (2015) 114 Metal-mediated nidine coupling

ix

The ZnII-mediated cyanamide–hydroxyguanidine coupling represents the first observation of interplay between any nitrile group and any hydroxyguanidine.

cyanamide–hydroxygua-

Frank Czerny, Peter Döhlert, Maik Weidauer, Elisabeth Irran, Stephan Enthaler Inorganica Chimica Acta 425 (2015) 118 Synthesis, characterization and application of nickel(II) complexes modified with N,N0 ,N00 -pincer ligands

Arnab Bhattacharya, Jnan Prakash Naskar, Smita Majumder, Rakesh Ganguly, Partha Mitra, Shubhamoy Chowdhury Inorganica Chimica Acta 425 (2015) 124 New mixed ligand oxorhenium(V) complexes of 3-thiapentane-1,5-dithiolato with 2-thiocytosine and 5-amino-1,3,4-thiadiazole-2-thiol: Experiment and theory

Róbert Uhrecky´, Ingrid Svoboda, ˇ ka Ru˚zˇicˇková, Marian Koman, Zden ˇ , Ján Pavlik, Ján Moncol, Lˇubor Dlhán Roman Bocˇa Inorganica Chimica Acta 425 (2015) 134 Synthesis, structure and magnetism of manganese and iron dipicolinates with N,N0 -donor ligands

Nickel(II) N,N0 ,N00 -pincer complexes with deprotonated N,N00 -substituted pyridine2,6-dicarboxamides ligands have been synthesized and characterized. In more detail, a square planar geometry for nickel hydroxido and nickel chlorido complexes was observed. The catalytic activity of Ni(II) complexes was investigated in the hydrosilylation of ketones.

The thermodynamic stability sequence of a series of Re(V) complexes both for [ReO(SSS)(HL1)] (1+) and [ReO(SSS)(L2)] (2) via the substitution reactions, ReO(SSS)SR + L3 fi ReOL3SR + SSS, (L3 = ligands having N, O and S donor atoms) have been undertaken for thermodynamic stability calculations in gas phase.

New ionic manganese(II/III), manganese(III) and iron(II/III) dipicolinates have been prepared and characterized by the single-crystal X-ray structure analysis and by magnetic susceptibility and magnetization measurements. A zero field splitting was found in the Mn(III) dipicolinates while an antiferromagnetic exchange interaction was present in the Fe(III) dipicolinates.

Ni(OTf) 2 O R

O

N NH

HN

R

Et 4 NOH

O R

N

N Ni OH

O Et 4N N

O N

R

O R1

CH 2Cl2

R

OH

cat. [Ni] R2

1. Ph2 SiH2 2. work-up

R1

R2

N Ni Cl

O Et4N N

R

x

Xue-Qin Song, Guo-Quan Cheng, Xiao-Run Wang, Wen-Yan Xu, Pan-pan Liu Inorganica Chimica Acta 425 (2015) 145 Structure-based description of a step-bystep synthesis of heterodinuclear ZnIILnIII complexes and their luminescence properties

William Henderson, Brian K. Nicholson, Ryland G. Fortney-Zirker, Sanjay Patel, Joseph R. Lane, Megan J. Wyllie, Edward R.T. Tiekink Inorganica Chimica Acta 425 (2015) 154 Further studies on the chemistry of tetramethylthiourea–platinum complexes: Evolution of cis-[PtCl{S@C(NMe2)2}(PPh3)2]+ to the dinuclear monothiocarbamato–sulfido complex [Pt2(l-S){l-SC(O)NMe2}(PPh3)4]+

Alexandre C. Bertoli, Ruy Carvalho, Matheus P. Freitas, Teodorico C. Ramalho, Daiana T. Mancini, Maria C. Oliveira, Amarílis de Varennes, Ana Dias

Contents

Stepwise course of the synthesis of ZnII– LnIII complexes with a new amide open crown ether ligand has been investigated through the determination of the intermediate and final products occurring in the process. The photoluminescent analyses show that the ligand to lanthanide energy transfer process is more effective in TbIII than that of EuIII, and the sensitized EuIIIand TbIII-based luminescence can be enhanced when ZnII ion is incorporated.

A novel dinuclear product [Pt2(l-S){lSC(O)NMe2}(PPh3)4]+ was obtained from refluxing cis-[PtCl2(PPh3)2] with tetramethylthiourea in the presence of tertiary amine base. The complex, which was structurally characterised, is also able to act as a metalloligand to organomercury(II) species, with DFT calculations suggesting coordination through the sulfido and carbonyl groups.

Structures proposals for the complex citrate–Zn2+ and identified by ESI-MS.

Inorganica Chimica Acta 425 (2015) 164 Theoretical and experimental investigation of complex structures citrate of zinc (II)

Jianlin Chen, Zhiguo Liu, Hao Feng, Yaoming Xie, R. Bruce King Inorganica Chimica Acta 425 (2015) 169 Binuclear 1,2-diaza-3,5-diborolyl iron carbonyls: Effect of replacing ring CC units with isoelectronic BN units

The binuclear 1,2-diaza-3,5-diborolyl iron carbonyl derivatives (Me4B2N2CH)2Fe2(CO)n (n = 5, 4, 3, 2) have been investigated by density functional theory for comparison with the corresponding (C5H5)2Fe2(CO)n systems. The lowest energy (Me4B2N2CH)2Fe2(CO)n (n = 4, 3, 2) structures have two bridging CO groups. A pentacarbonyl (Me4B2N2CH)2Fe2(lCO)(CO)4 with a bridging CO group as the only link between the two halves of the molecule is found.

Cl

C Pt P

S

P

N Me3N, MeOH reflux

Pt

Pt

S O

S C N

Contents

Basu D. Panthi, Stephen L. Gipson, Andreas Franken Inorganica Chimica Acta 425 (2015) 176 Structural studies of some rhodium(III) acyl complexes containing bidentate phosphines

Mark B. Bushuev, Yuri V. Gatilov, Viktor P. Krivopalov, Oleg P. Shkurko Inorganica Chimica Acta 425 (2015) 182 Tetra- and polynuclear cadmium(II) complexes with 3,5-bis(pyrimidin-2-yl)-4H1,2,4-triazol-4-amine. Synthesis, polymorphism, lone pair–p interactions and luminescence

Leonid N. Bochkarev, Yulya P. Bariniva, Alena I. Ilicheva, Sergey Yu. Ketkov, Evgenii V. Baranov, Vasilii A. Ilichev, Dmitry G. Yakhvarov Inorganica Chimica Acta 425 (2015) 189 Synthesis, crystal structures and luminescent properties of the copper(I) pyrazolonate complexes

Matthew D. Le Page, Brian O. Patrick, Steven J. Rettig, Brian R. James Inorganica Chimica Acta 425 (2015) 198 2-Pyridyl-phosphine and -diphosphine complexes of nickel(II), and their aqueous solution chemistry

xi

Ten rhodium(III) acyl complexes of the type Rh(diphosphine)(COR)I2 have been synthesized and characterized by X-ray crystallography. All display square pyramidal geometry with orientation of the apical acyl group determined by CH  O hydrogen bonding of the acyl with the diphosphine.

A series of cadmium(II) complexes, [CdLCl2]n (1), a-{[CdLCl2]ÆH2O}n (2), b{[CdLCl2]ÆH2O}n (3), and [Cd4L2(H2O)2Cl8]Æ2H2O (4), with 3,5-bis(pyrimidin-2yl)-4H-1,2,4-triazol-4-amine (L), have been synthesized. Lone pair–p interactions between Cl atom and the triazole ring were observed in the structure of [Cd4L2(H2O)2Cl8]Æ2H2O. The complexes b-{[CdLCl2]ÆH2O}n and [Cd4L2(H2O)2Cl8]Æ2H2O show blue emission in the solid state.

New copper(I) pyrazolonate complexes were synthesized and structurally characterized. Their photo- and electroluminescent properties were investigated. The compounds were found to reveal electroluminescence of yellowish-orange and yellow colors.

The synthesis and coordination chemistry (especially dissolution in water) of the above NiII species containing 2-pyridylphosphine and 2-pyridyl-diphosphines are extended. Seven X-ray structures are reported.

Electroluminescence (1): 286 cd/m2

[Cu(Pri -PMP)(DPEphos)] - 1

CIE: 0.52/0.46 (2): 39 cd/m2

t

[Cu(Bu -PMP)(DPEphos)] - 2

CIE: 0.45/0.45

PPh3 P

X--- Ni X

P

X

P Ni

X

PPh3

X = halogen, NCS, NO3

P P

H2O

Ni(H2O)6

H2O

2+

slow

H2O

P

P = py2P(CH2)2Ppy2 or

2+

py2P[CH(CH2)3CH]Ppy2

Ni

py = 2-pyridyl

P 2+

-

and NiCl2(P,N PN3), [Ni(N,N',N'' PN3)2] 2Cl ; PN3 = Ppy3

xii

Sandeepta Saha, Ashok Sasmal, Chirantan Roy Choudhury, Guillaume Pilet, Antonio Bauzá, Antonio Frontera, Sharmila Chakraborty, Samiran Mitra Inorganica Chimica Acta 425 (2015) 211 Synthesis, crystal structure, antimicrobial screening and density functional theory calculation of nickel(II), cobalt(II) and zinc(II) mononuclear Schiff base complexes

Emily M. Low, Robert L. LaDuca Inorganica Chimica Acta 425 (2015) 221 Luminescent zinc aliphatic dicarboxylate coordination polymers with bis(4-pyridylmethyl)piperazine: Effect of chain length and steric bulk on topology and water molecule aggregation

Bradley W. Smucker, John Bacsa, Jitendra K. Bera, Eric W. Reinheimer Inorganica Chimica Acta 425 (2015) 233

Contents

Three new monomeric Schiff base complexes of Ni(II), Co(II) and Zn(II) have been synthesized. These complexes form 3D supramolecular motif by means of hydrogen bonding and p–p interaction. The energetic of these interactions are also evaluated with theoretical DFT calculations. The biological properties such as antimicrobial and antibacterial activity of the complexes are also studied which show a significant result.

Zinc aliphatic dicarboxylate coordination polymers containing the long-spanning tethering ligand bis(4-pyridylmethyl)piperazine (4-bpmp) show 2D and interpenetrated 3D topologies depending on dicarboxylate length and substituents. [Zn(adipate)(4-bpmp)]n (pictured) possesses a system of 5-fold interpenetrated diamondoid nets.

Three dirhenium complexes are equatorially bridged by tetrathiafulvalene-monocarboxylate.

Redox-active TTF carboxylate as an axial bridging ligand for dirhenium metal–metal bonded complexes

Balasubramaniam Arul Prakasam, Manu Lahtinen, Anssi Peuronen, Manickavachagam Muruganandham, Erkki Kolehmainen, Esa Haapaniemi, Mika Sillanpää Inorganica Chimica Acta 425 (2015) 239 Spectral and structural studies on Ni(II) dithiocarbamates: Nickel sulfide nanoparticles from a dithiocarbamate precursor

NMR spectral and single crystal X-ray structural studies on three new Ni(II) dithiocarbamates have been reported. Solvothermal preparation of nickel sulfide nanospheres from dithiocarbamate precursor is also reported and the product was analyzed by XRD, SEM and TEM.

Contents

Khaled A. Shennara, Ray J. Butcher, Frederick T. Greenaway Inorganica Chimica Acta 425 (2015) 247 Co(II), Cu(II), Mn(II) and Ni(II) complexes of maleic hydrazide

Yang-Hui Luo, Qing-Ling Liu, Yang Ling, Li-Jing Yang, Wei Wang, Bai-Wang Sun Inorganica Chimica Acta 425 (2015) 255 Guest molecules dependent structures, intermolecular interactions and magnetic properties of iron (II) polymer with 4,40 dipyridyl disulfide

Girijesh Kumar, Gulshan Kumar, Rajeev Gupta Inorganica Chimica Acta 425 (2015) 260 Asymmetrical metalloligands based {Co3+– Cd2+} and {Co3+–Ag+} coordination polymers: Syntheses and characterization

Xiuli Wang, Lufei Chen, Jingjing Cao, Guocheng Liu, Hongyan Lin Inorganica Chimica Acta 425 (2015) 269 Assembly of various reduced molybdophosphate-based cadmium complexes by controllable in situ ligand transformation

Maleic hydrazide binds as a unidentate ligand to Co(II) and Ni(II) through a ring nitrogen atom but to Cu(II) and Mn(II) through a phenolate oxygen atom. All complexes have octahedral geometries with four water ligands except the Cu(II) complex which has a square pyramidal geometry with three water ligands.

xiii

Co(3,6-dihydroxypyridazine)2(H2O)4

Cu(3,6-dihydroxypyridazine)2(H2O)3

The change of water molecules by 2,5dichloropyrazine molecule for an iron (II) coordination polymer with 4,40 -dipyridyl disulfide (4-DPS) ligands tuned the crystal structures, intermolecular interactions and magnetic properties.

Two asymmetrical metalloligands 1 and 2 offering distinct appended pyridyl groups have been utilized to synthesize {Co3+– Cd2+} (3 and 4) and {Co3+–Ag+} (5 and 6) heterometallic coordination polymers.

Two novel 1D P4Mo6-based metal–organic complexes constructed from the classic sandwich-type [Cd(P4Mo6)2] dimers and Cd2+ ions or trinuclear {K2Cd(H2O)6} fragments have been synthesized. In situ bpp transformation has been observed. The reaction conditions play important roles in the in situ syntheses of different tetradentate tpb and tpc from the same precursor bpp. The electrocatalytic activity of compound 2 may make it a candidate for potential catalytic material.

R'

R

R'

R -

N N (1)

O

N

R N R' O

Co

N

O N R' N R

N

O

N N (2)

xiv

Contents

Vladislav A. Tuskaev, Svetlana Ch. Gagieva, Dmitrii A. Kurmaev, Nikolay A. Kolosov, Ivan V. Fedyanin, Boris M. Bulychev Inorganica Chimica Acta 425 (2015) 275 Titanium (IV) complexes stabilized by 2, 6-bis-(a,a0 -diphenyl(hydroxy)methyl)-pyridine: Catalytic activity in olefin polymerization and impact of lithium and magnesium chlorides

Newly titanium complexes bearing 2,6-bis(a,a0 -diphenyl(hydroxo)methyl)-pyridine ligand were synthesized. The crystal structure of titanium complexes 2, 5, 10 were determined by X-ray crystallography. Individual complexes 2–5 are active in ethylene and 1-hexene polymerization only in the presence of Et2AlCl/ Bu2Mg binary co-catalyst. The pre-catalysts formed in situ, containing LiCl or MgCl2, are active in polymerization when activated by methylalumoxane or trimethylaluminum (TMA). Ability of Li and Mg derivatives to improve the catalytic ability of pre-catalysts.

Ph

Ph N

Ph OH

Ph OH

Ti4+ L' O Ti

N O

O

L

R

H

H

L - Cl, OiPr L' - HOiPr R = H, C4H9

Highly active only with Et2AlCl/Bu2Mg

Cl Ti

N

L

H

1. BuLi or Bu2Mg 2. TiCl4

O

+ LiCl

or

Cl MgCl2

in situ catalyst H

R

H

H

Highly active with MAO, TMA or Et2AlCl/Bu2Mg

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