Inorganic Chemistry Communications (v.7, #3)

Contents list (iii-vi).

Size-controllable sonochemical synthesis of thermoelectric material of Bi2Se3 nanocrystals by Xiao-feng Qiu; Jun-Jie Zhu; Lin Pu; Yi Shi; You-Dou Zheng; Hong-Yuan Chen (319-321).
We report the sonochemical synthesis of thermoelectric materials of Bi2Se3 nanocrystals in the 6.9–15.2 nm size regime. In this method, the size of Bi2Se3 nanocrystals can be easily controlled by varying the concentration of EDTA in aqueous solution.
Keywords: Thermoelectric materials; Bi2Se3; Sonochemistry; Nanocrystals;

Preparation and characterization of the CdS/PSA core-shell “egg” by Chunnian Chen; Chunling Zhu; Linyun Hao; Yuan Hu; Zuyao Chen (322-326).
CdS/PSA (Poly(styrene–co-acrylic acid) (St/AA)) core-shell composites “egg” whose major and minor axis is about 400, 200 nm, respectively, have been prepared using PSA ellipsoids as template. Viscoelastic deformation of polyvinyl alcohol was used to convert monodispersed PSA microspheres into uniform ellipsoids with a tightly controlled major-to-minor axis ratio.
Keywords: Composites; CdS; PSA; Ellipsoids; Core-Shell; Egg;

A polymeric structure of magnesium dithiodiglycolate: [Mg(C4H4O4S2)H2O] n by Quanzheng Zhang; Canzhong Lu; Wenbin Yang (327-329).
A novel magnesium dithiodiglycolate, [Mg(C4H4O4S2)H2O] n , was synthesized from the aqueous solution of Mg(ClO4)2 and mercaptoacetic acid. The complex structure consists of two-dimensional (2D) layers, which are further linked up through weak S–S supramolecular interactions into a three-dimensional (3D) framework.
Keywords: Mercaptoacetic acid; S–S supramolecular interaction; Polymeric magnesium dithiodiglycolate;

Copper(II) complexes with a novel tris(3,5-diisopropyl-1-pyrazolyl)methane ligand, [Cu(X2){HC(3,5-iPr2pz)3}] (X=Cl and NO3) by Kiyoshi Fujisawa; Tetsuya Ono; Hijiri Aoki; Yoko Ishikawa; Yoshitaro Miyashita; Ken-ichi Okamoto; Hiroshi Nakazawa; Hideyuki Higashimura (330-332).
The synthesis of a novel tris(3,5-diisopropyl-1-pyrazolyl)methane ligand, HC(3,5-iPr2pz)3, is described; the structures of chlorocopper(II) and nitratocopper(II) complexes with its ligand have been determined by X-ray crystallography and compared with those of the related copper(II) complexes with HB(3,5-iPr2pz)3 .
Keywords: Copper(II); Hydrotris(pyrazolyl)borate; Tris(pyrazolyl)methane; Mononuclear complex; Crystal structure;

The novel non-covalent aggregation, formed by charge-transfer interaction between dihydroxymethyl-di-(2-pyrrolyl)methane (2) and TCNQ (1) in polar solvent, may be used as a colorimetric chemosensor for high selective detection of PO4 3− and CO3 2− inorganic anions in aqueous solution.A new class of non-covalent charge-transfer complex, formed by dipyrromethane and tetracyanoquinodimethane (TCNQ), is characterized. As colorimetric anion sensors, the assembly of dihydroxymethyl-di-(2-pyrrolyl)methane and TCNQ may be used for higher selective detection of PO4 3− and CO3 2− than other inorganic anions in MeCN/H2O (1:1, v/v) solvent system.
Keywords: Anion detection; Charge-transfer complex; Sensor; TCNQ;

A tridentate ligand for preparation of bisterpyridine-like ruthenium(II) complexes with an increased excited state lifetime by Henriette Wolpher; Olof Johansson; Maria Abrahamsson; Mikael Kritikos; Licheng Sun; Björn Åkermark (337-340).
A new tridentate polypyridine ligand, 6-(2-picolyl)-2,2-bipyridine, as well as its homoleptic Ru(II) complex has been prepared. Photophysical studies show a prolonged lifetime of the excited state compared to [Ru(tpy)2]2+, where tpy is 2,2:6,2″-terpyridine.
Keywords: Ruthenium modified terpyridine complex; Excited state lifetime;

New pyridine adducts of organosilanols by Y.K. Gun’ko; V.G. Kessler; R. Reilly (341-343).
The reaction of Ph2Si(OH)2 (1) with pyridine led to the formation of the pyridinium adduct (HO)Ph2SiOSiPh2O(PyH) (2). The complex contains one free silanol group and another silanol group is bonded to the amine via hydrogen bonding. The analogous reaction of (c-C6H11)7Si7O9 (OH)3 (3) with pyridine afforded the salt [PyH][{(c-C6H11)7Si7O9(OH)2}2H] (4). Both pyridinium derivatives have been characterised by X-ray diffraction. In complex 4 the anion consists of two silsesquioxane fragments connected by intermolecular hydrogen bonding.
Keywords: Silanols; Silsesquioxanes; Pyridine; Molecular structure;

Indium hollow spheres and nanotubes were successfully synthesized via a simple template-free solvothermal route at different temperatures. The products were characterized by X-ray powder diffraction and transmission electron microscopy.
Keywords: Indium; Hollow spheres; Nanotubes; Solvothermal;

The reaction of MnCl2 and glutaric acid in aqueous solution affords a new 3D Mn-glutarate with an empirical formula of Mn3(H2O)[CO2(CH2)3CO2]3 (1). The structure of 1 contains honeycomb-type 12 membered Mn–O–Mn networks of MnO6 octahedra and interconnecting Mn–O–C–O–Mn bridging resulting in magnetic interaction below 3 K.
Keywords: Crystal structure; 3D network; Glutarate; Magnetic properties;

A unique 2-D coordination network sandwiched by alternating 1-D intra-hydrogen bonding networks has been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction technique and thermal analysis. [(H2O)Mn(BN)2] (BN = bromonicotinato) crystallized in monoclinic crystal system, space group P21/c with unit cell dimensions a=10.385(1), b=10.151(1) and c=7.156(1) Å, β=98.119(1)°, Z=2.
Keywords: Coordination polymer; One-dimensional; Two-dimensional; Hydrothermal reaction; Covalent network; Hydrogen bond;

An unexpected in situ formation of a substitute tetrazole ligand and its Mn(II) and Cu(II) complexes by Xiao-Jie Mo; En-Qing Gao; Zheng He; Wen-Jun Li; Chun-Hua Yan (353-355).
The reaction of 2-aminomethylpyridine, benzaldehyde and NaN3 in the presence of the metal ions leads to an unexpected in situ formation of a substituted tetrazole, 5-(2-pyridyl)-1H-tetrazole, and its Mn(II) and Cu(II) compounds MnL2(H2O)2 (1) and CuL2(H2O)2 (2). In these structures, mononuclear units connect each other via hydrogen bonds to form a two-dimensional network.
Keywords: In situ formation; Tetrazole; Azide; Hydrogen bond;

A new polymer (C5H9NO2)2[La(H2O)7CrMo6H6O24] · 11H2O (1), has been synthesized and structurally characterized. Compound 1 exhibits a novel one-dimensional (1-D) chain-like structure consisting of Anderson-type polyoxoanions hexamolybdochromate [CrMo6H6O24]3− covalently linked by hydrated La3+ ions, furthermore pseudo-2-D layers can be formed owing to the strong (La)OH2⋯O hydrogen bonds among adjacent chains.
Keywords: Chain-like polymer; Lanthanum ion; Hexamolybdochromate; Proline;

Solution-phase synthesis of Ag2S hollow and concave nanocubes by Mengdong Wu; Xinxin Pan; Xuefeng Qian; Jie Yin; Zikang Zhu (359-362).
Hollow and concave Ag2S nanocubes have been prepared through the reaction of thioacetamide (TAA) and AgNO3 in carboxymethyl cellulose (CMC) aqueous solution. CMC acts as the templates and capping agents in the solution. The edge length of each cube was about 200 ± 50 nm.
Keywords: Ag2S; Nanocubes; Hollow; Concave;

The hydrothermal reaction of Na2WO4  · 2H2O, CuSO4  · 5H2O, 2,2:6,2″-terpyridine (terpy), H3PO4 and H2O at 150 °C for 120 h yielded a mixture of [{Cu4(terpy)4(PO4)(H2O)2}{W12O36(PO4)}] · 5H2O (1  · 5H2O) and [{Cu(terpy)(H2O)2}2{W12O36(PO4)}] · 6H2O (2  · 6H2O). The structure of 2 consists of discrete {W12O36(PO4)}4− Keggin clusters whose surface is decorated by two {Cu(terpy)(H2O)}2+ charge-compensating subunits. In contrast, the structure of 1 is one-dimensional with the chain constructed from {W12O36(PO4)}5− Keggin clusters and the cationic {Cu4(terpy)4(PO4)(H2O)2}5+ clusters. Both materials are mixed valence. In the case of 1, the tungstate core is formally {W10(VI)W2(V)}, while for 2 the oxidation states are {W11(VI)W(V)}. Crystal data: C30H27N6Cu2W6O24.5P (1  · 5H2O), monoclinic, C2/c, a=14.5025(6) Å, b=22.2102(9) Å, c=26.566(1) Å, β=101.813(1)°, V=8375.6(6) Å3, Z=8. C15H21N3CuO25W6P0.5 (2  · 6H2O), monoclinic, C2/c, a=17.6263(9) Å, b=16.6990(9) Å, a=22.944(1) Å, β=112.285(1)°, V=6249.0(6) Å3, Z=8.
Keywords: Polyoxotungstate; Building block approach to oxides; Tetranuclear copper phosphate cluster; Mixed valence materials;

Chirality of a Strandberg-type heteropolyanion [S2Mo5O23]4− by Vaddypally Shivaiah; T. Arumuganathan; Samar K. Das (367-369).
The heteropolyanion [S2Mo5O23]4− having C 2 symmetry is dissymmetric and hence expected to be chiral. The heteropoly-compound [NMe4]4[S2Mo5O23] exhibits its both enantiomers in DMSO solution by a Pfeiffer effect when l- and d-arabinose are used as environment substances.
Keywords: Strandberg type heteropolyanion; Recemic mixtures; Circular dichroism studies; Pfeiffer effect;

Semiconductor zinc chalcogenides nanofibers from 1-D molecular precursors by Yajie Dong; Qing Peng; Yadong Li (370-373).
The reaction of zinc (Zn) and sulfur (S) or selenium (Se) with hydrazine hydrate (N2H4  · H2O) at 80 °C leads to the formation of N2H4 intercalated lamellar zinc chalcogenides which are characterized by classical methods and shown to be self-assembled into 1-D morphologies; decomposition of these molecular precursors in ethanol at 180 °C results in high temperature stable wurtzite ZnS or ZnSe nanofibers.
Keywords: Zinc chalcogenides; Nanofibers; 1-D molecular precursors; Intercalated lamellar structures;

Self-assembly of Co(NO3)2 and N,N -bis(4-pyridylcarbonyl)-4,4-diaminodiphenyl ether (L), a dipyridyl-based ligand separated by phenyl amide spacer, afforded an interpenetrating Co(II) coordination polymer {[CoL 2(NO3)2] · 2(C2H5) 2 O · (CH3)2SO · H2O} n (1). X-ray analysis of 1 shows that a unique combination of coordination and hydrogen bonds within a framework gives this material a spacious multi-channel structure. Moreover, the crystalline framework of 1 is virtually unchanged after removing the solvent molecules from the channels resulting in a nanoporous structure with estimated free volume of 31.4%.
Keywords: Dipyridyl ligand; Cobalt(II); 3-D coordination polymer; X-ray crystal structure; Interpenetrating framework; Multi-channels; Nanoporous structure;

A new co-ordination framework {[Zn(Ac)2(bbbm)](CH3OH)2} n has been prepared and characterized by single crystal X-ray diffraction and Z-scan technique. The polymer has a helical chain structure formed by bbbm linking two adjacent Zn(II) ions and exhibits strong NLO refraction property with n 2 value of 1.38×10−17 m2  W−1, which can match those of the best known third-order NLO materials such as inorganic oxides, semiconductors, and cluster compounds.A new co-ordination framework {[Zn(Ac)2(bbbm)](CH3OH)2} n (1) (bbbm=1,1-(1,4-butanediyl)bis-1H-benzimidazole) has been synthesized and structurally characterized by single crystal X-ray diffraction and Z-scan technique. The polymer has a one-dimensional single helical chain structure formed by bbbm linking two adjacent Zn(II) ions and exhibits strong NLO refraction property with n 2 value of 1.38×10−17 m2  W−1, which can match those of the best known third-order NLO materials such as inorganic oxides, semiconductors, and cluster compounds.
Keywords: Zinc; Crystal structure; Coordination polymer; Helical; Nonlinear optical property;

The copper(II) complex [(3-AMP)(3-Ac-AMP)Cu](ClO4)2 (3) was obtained by the reaction of 3-amino-5-methylpyrazole (3-AMP, 1) with Cu(ClO4)2 in acetonitrile. The reaction involves the amidation of acetonitrile under mild conditions and thus provides a new entry into amidation chemistry. Furthermore, complex [(3-Ac-AMP)Cu](ClO4)2 (4) was obtained from the reaction of 3-acetamido-5-methylpyrazole (3-Ac-AMP, 2) with Cu(ClO4)2. Both complexes were analyzed by single crystal X-ray crystallography, which establishes the nature of the complexes. The Cu in complex 3 is in a distorted trigonal bipyramidal environment, whereas the metal in complex 4 is in a square-planar environment.
Keywords: Pyrazole; Nitrile amidation; Copper; Catalysis;

Nano-sized La x Bi(2–x)Te3 (x=0.1–0.5) powders have been synthesized in ethanol solutions at 120–180 °C for 12–48 h. It is found that the La x Bi(2–x)Te3 compounds have the same crystal structure and similar lattice constants as the binary Bi2Te3 compound.
Keywords: Chemical synthesis; Bismuth telluride; Rare-earth element; Thermoelectric materials;

Photoluminescence and combustion synthesis of CaMoO4 doped with Pb2+ by Ping Yang; Guang-Qing Yao; Jian-Hua Lin (389-391).
The photoluminescence (PL) and combustion synthesis of CaMoO4 doped with Pb2+ were investigated. Combustion synthesis resulted in an enhancement of the luminescence intensity of CaMoO4:Pb2+ with their more narrow particle size distribution.
Keywords: Photoluminescence; Combustion synthesis; CaMoO4; Pb2+;

The fluorescent intensity of the probe molecule methylene blue (MB) increases drastically when Zn(II) ion is added to the MB–DNA solution system, which indicates that some intercalated MB molecules are released due to the binding of Zn(II) ions to the DNA base pairs.
Keywords: Zinc(II); DNA; Intercalative binding; Spectroscopy; Photobleaching;

Terephthalate bridged frameworks of Nd and Sm Phthalates by A. Thirumurugan; Srinivasan Natarajan (395-399).
A hydrothermal reaction of terephthalic acid (1,4-benzenedicarboxylic acid, 1,4-BDC), M2O3 (M=Nd and Sm) 1,2-dicyanobenzene (1,2-DCB), produced a metal-organic coordination polymer of the formula, M2(H2O)4[(1,2-BDC)2(1,4-BDC)], (M=Nd and Sm). The phthalate anion, found in the final product was generated in situ during the synthesis by the hydrolysis of 1,2-DCB. The M atoms show differences in the coordination environments. The structure is built-up by the rare-earth phthalate layers cross-linked by the terephthalate anions giving rise to three-dimensional structure with one-dimensional rectangular channels. The bound water molecules project into these channels. Both the compounds exhibit photoluminescence.
Keywords: Benzenedicarboxylate; Mixed ligands; Lanthanide; Metal-organic frameworks;

The salt Ag+SbF6 shows a greenish-yellow luminescence (λ max=528 nm) which originates from a AgI  → SbV metal-to-metal charge transfer triplet.
Keywords: Electronic spectra; Photoluminescence; Charge transfer; Silver; Antimony;

Two coordination polymers, [Cd(isonicotinate)2(H2O)] · DMF (1) and Cd3(isonicotinate)4(NO3)2(4,4-bipy)2(H2O)2 (2) have been synthesized and characterized. Both compounds adopt 3-D frameworks, built up by two sets of interpenetrated fragments. TGA studies indicated 1 is porous and its DMF and coordinated water molecules can be removed upon heating.
Keywords: Coordination polymer; Isonicotinate; Interpenetrated; Porous;

X-ray crystal structure, ESR and potentiometric studies of copper(II) complexes with (2-pyridylmethyl, 3-pyridylmethyl) amine ligand by Mathieu Soibinet; Isabelle Déchamps-Olivier; Aminou Mohamadou; Michel Aplincourt (405-409).
In this paper, we describe the coordinating behaviour of the (2-pyridylmethyl, 3-pyridylmethyl) amine ligand with the copper(II) ion. This ligand is bidentate and forms, in accordance with the pH values, 1:1 and 1:2 species (ratio metal:ligand). These species were characterized in aqueous solution by ESR spectroscopy and their overall stability constants were determined by potentiometric measurements. In solid state, we obtained the compounds [CuLHCl2](BF4) and [CuL2](BF4)2. In ESR spectroscopy, the first compound is characterized by an axial g tensor (g =2.268 and g =2.091), whereas the second one is characterized by a rhombic g tensor (g 1=2.185, g 2=2.146 and g 3=2.026). We crystallized the [CuLHCl2]Cl compound, in hydrochloric medium, from the [CuLHCl2](BF4) powder. The compound obtained is a pseudo octahedral dimeric system, in which each copper(II) is surrounded by two nitrogen atoms and four chloride ions. The intramolecular Cu–Cu distance is 3.859 Å.
Keywords: X-ray crystal structure; Stability constants; EPR; Cu(II) complexes; Dimeric system;

Synthesis and structure of a bridging dimer of PhBi[O2CCH(CH3)CH2GePh3]2 by Lin Yu; Yong-Qiang Ma; Run-Chang Liu; Guo-Cang Wang; Jin-Shan Li (410-411).
The novel compound PhBi[O2CCH(CH3)CH2GePh3]2 has been synthesized and characterized structurally. The molecular structure shows that both carboxylates are bidentate ligands and oxygen bridges between symmetrically related molecules link them into dimer.
Keywords: Bismuth; Germanium; Dimer; Crystal structure;

The reaction of 1,1-diaminoferrocene 1 with 1,2-bis(chlorodimethylsilyl)ethane in the presence of triethylamine leads to the ferrocene derivative 5 bearing in 1-position the amino group and in 1-position an azadisilacyclopentyl ring. Complex 5 is shown to be in equilibrium with the 1,6,2,5-diazadisila-[6]ferrocenophane 6. Both complexes 5 and 6 were characterised by X-ray structural analysis, and in solution by 1H, 13C and 29Si NMR spectroscopy.
Keywords: Ferrocenes; 1,1-Disubstituted; [6]Ferrocenophanes; Silicon; NMR; X-ray;

In situ polymerization template route to CdSe hollow spheres under UV irradiation by Xu Zhang; Yi Xie; Fen Xu; Di Xu; Xiaohui Liu (417-419).
CdSe hollow spheres are successfully obtained via an in situ polymerization template route under the ultraviolet irradiation and the possible formation mechanism is discussed.
Keywords: CdSe; Template; Hollow spheres; Polymerization;

Each molecule of the cis and trans conformations of the new complex [NiL] recognizes a molecule of its enantiomer to form a dimer through unprecedented π⋯π interactions between a phenyl ring and four separate unclosed π-systems.
Keywords: Macrocyclic compound; Nickel(II) complex; π⋯π interaction; Enantiomer;

Synthesis and X-ray crystal structures of [pyH][Fe(pic)2Cl2] and [Fe22-OMe)2(pic)4] (Hpic=2-picolinic acid) by Sneh L. Jain; Pravat Bhattacharyya; Heather L. Milton; Alexandra M.Z. Slawin; J. Derek Woollins (423-425).
The passage of dichlorine gas through a dichloromethane solution of [Fe(pic)2(py)2] gives [pyH][Fe(pic)2Cl2] (1) whilst the methoxy bridged diiron(III) complex 2 was prepared and crystallised directly from the reaction of [Fe(pic)2(py)2] with methanol in air. The X-ray structures of 1 and 2 are reported.
Keywords: Coordination chemistry; Iron; Gif catalysts; Crystal structure;

rac-[SP-4-2]-{2-[(dimethylamino-κN)methyl]phenyl-κC 1}{[2-(diphenylphosphanyl-κP)ferrocenyl](methoxycarbonyl)methyl-κC}palladium(II) (1) was synthesized by deprotonation of [SP-4-4]-chloro{2-[(dimethylamino-κN)methyl]phenyl-κC 1}{rac-methyl 2-(diphenylphosphanyl)ferrocenylacetate-κP}palladium(II) with t-BuOK. Complex 1 was characterized by spectral methods and its reactivity studied. The structure of 1 was determined by X-ray crystallography and discussed in relation to other complexes with phosphanoalkyl ligands derived from phosphanoacetic esters.
Keywords: Palladium; Phosphinoester ligands; Alkyl complexes; Ferrocene; X-ray crystallography;

Preparation and morphology of magnesium titanate nanofibres via electrospinning by N. Dharmaraj; H.C. Park; B.M. Lee; P. Viswanathamurthi; H.Y. Kim; D.R. Lee (431-433).
Magnesium titanate/polyvinyl acetate composite nanofibres were prepared by sol–gel processing and electrospinning technique. Phase pure magnesium titanate fibres of 200–400 nm diameter were obtained by high temperature calcination of the inorganic–organic composite fibres. The magnesium titanate nanofibres thus prepared have been characterized by SEM, XRD and FT-IR, respectively. The surface morphology and crystallization of magnesium titanate fibres were found to depend on the calcination temperature.
Keywords: MgTiO3nanofibres; Sol–gel processing; Electrospinning; Calcination; PVAc;

Self-assembly of a Cu(II)–Ba(II) 2D coordination polymer containing decanuclear 28-membered metallocycles by Wen-Long Liu; Yang Zou; Chang-Sheng Lu; Chun-Lin Ni; Dong-Bin Dang; Yi-Zhi Li; Qing-Jin Meng (434-436).
A novel heterometallic 2D coordination polymer, {[Ba(H2O)4(CuL)2]} (1) (H3L=N-2-hydroxyacetophenoneglycylglycine), was synthesized by self-assembly between metalloligands [CuL] and the Ba(II) ions. The structure reveals the polymer contains hexanuclear building blocks, which are connected to form 28-membered decanuclear metallocycles, and are assembled further into 2D network structure.
Keywords: Metalloligand; Heterometallic macrocycle; Copper–barium; Dipeptide; Crystal structure;

A novel polyoxovanadate [{Ni(quaterpy)(H2O)}2V4O12] · 10H2O (1) (quaterpy =2,2;6,2″;6″,2′′′-quaterpyridine) has been hydrothermally synthesized and structurally characterized. The title compound consists of tetranuclear V4O12  4− clusters grafted with [Ni(quaterpy)(H2O)]2+ complex. Compound 1 represents the first polyoxometalate decorated with quaterpy ligand.
Keywords: Hydrothermal synthesis; Dehydrogenative coupling; Crystal structure; Polyoxovanadate;

2-Pyridineformamide thiosemicarbazone (HL1) reacts with UO2(NO3)2  · 6H2O or [NBu4]2[UO2Cl4] under deprotonation and formation of neutral uranyl complexes. The composition of the products is dependent on the solvents used: [UO2(L1)(OH)]2 is formed when acetonitrile is used, whereas the hydrogen-bonded dimer [UO2(L1)(MeO)(MeOH)]2 is the product in methanol. Both products have been studied by X-ray crystallography showing uranium–uranium distances of 3.750 and 5.385 Å.
Keywords: Uranium; Thiosemicarbazones; Actinides; Crystal structure;

Reversible π-coordination of triallylphosphine in a trinuclear ruthenium carbonyl cluster by Anders Thapper; Emma Sparr; Brian F.G. Johnson; Jack Lewis; Paul R. Raithby; Ebbe Nordlander (443-446).
The triallylphosphine-substituted clusters [Ru3(CO)11{P(CH2CH=CH2)3}], [Ru3(CO)10{P(CH2CH=CH2)3}2] and [Ru3(CO)10{σ;π-CH2 =CHCH2P(CH2CH=CH2)2}] have been prepared; reaction of [Ru3(CO)10{σ;π-CH2 =CHCH2P(CH2CH=CH2)2}] with phosphines/phosphites leads to cleavage of the Ru–allyl π-bond and formation of [Ru3(CO)11{P(CH2CH=CH2)3}(PR3)].
Keywords: Cluster; Hemilabile ligand; Allylphosphine;

Synthesis of porous silica structures with hollow interiors by templating nanosized calcium carbonate by Jian-Feng Chen; Jie-Xin Wang; Run-Jing Liu; Lei Shao; Li-Xiong Wen (447-449).
Shape-controlled porous silica structures with hollow interiors were synthesized by using CaCO3 nanoparticles with the corresponding morphologies and sizes as the inorganic templates. Through the hydrolysis of sodium silicate, a continuous coating of SiO2 was deposited over the surface of CaCO3 cores to form core–shell structures. Hollow silica structures were finally obtained after calcining process and dissolving CaCO3 in HCl dilute solution. The as-prepared hollow products were characterized with TEM, SEM, EDS, BET, and FT-IR.
Keywords: Nanosized calcium carbonate; Shape control; Hollow silica; Core–shell structure;

A new 2D heterometallic Cu/Cd mixed-anion polymer with dicyanamide and thiocyanate bridges formed via the reaction of elemental copper, cadmium dicyanamide and ethylenediamine by Oksana V Nesterova (Pryma); Svitlana R Petrusenko; Vladimir N Kokozay; Brian W Skelton; Wolfgang Linert (450-454).
The new heterometallic 2D polymer [Cu(en)2Cd(dca)2(SCN)2] n (en=ethylenediamine; dca=dicyanamide, N(CN)2 ), the first example of a compound containing the unique mixed-anion Cd(dca)2(SCN)2 2− fragment, has been prepared from copper powder, cadmium dicyanamide, ammonium thiocyanate and ethylenediamine in methanol solution in air. The polymeric sheets of the compound comprise two different rings – 28-membered [Cu2Cd41,5-dca)21,3-NCS)4] macrocycles in which two 12-membered [Cd21,5-dca)2] rings form sections.
Keywords: Heterometallic complex; Dicyanamide; Thiocyanate; Elemental copper; Ethylenediamine; Crystal structure;

The unprecedented template action of ytterbium ion in the synthesis of pentaaza macrocyclic Schiff bases is exemplified by isolation and definitive identification of the seven-coordinate pentagonal bipyramidal complex of formula [YbLCl2]ClO4 (1), where L is 2,14-dimethyl-3,6,10,13,19-pentaazabicyclo[13.3.1.]nonadeca-1(19),2,13,15,17-pentaene, providing the first example of crystallographically characterized pentaaza macrocyclic ytterbium complex. This complex is capable of forming the dimeric peroxo [Yb2L2(μ-η22-O2)Cl2](ClO4)2 (2) derivative containing the biologically significant planar side-on doubly bidentate coordination mode of the peroxide. In the crystal structure, inclusion of the appropriate solvent molecule generates supramolecular architecture in which the solvent-controlled self-assembly is observed.
Keywords: Schiff base pentaaza macrocycles; Ytterbium complexes; Peroxo ligands; Supramolecular self-assembly; Template synthesis; X-ray structure;

A novel neutral arylnickel(II) phosphine complex 1 bearing 2-oxazolinylphenolato ligand is synthesized by the reaction of trans-Ni(Ph)(Cl)(PPh3)2 with 2-(4,5-dihydro-oxazol-2-yl)phenol in the presence of NEt3, and the molecular structure is determined by X-ray single crystal diffraction. Complex 1 exhibits high activity and selectivity in catalyzing olefin oligomerization when various organoaluminum cocatalysts or Ni(COD)2 are used (TOF values up to 507 kg oligomers/(mol Ni · h)).
Keywords: Nickel complex; Oxazoline ligand; Crystal structure; Olefin oligomerization;