Inorganic Chemistry Communications (v.4, #10)

Announcing “Mini-Reviews” by Umberto Belluco; Daniel G Nocera; Albert S.C Chan (v).

Inorganic composite CdS/heteropolyanion nanoparticles with salt-like structures by Degang Fu; Yu Zhang; Juzheng Liu; Zuhong Lu (527-529).
Using the reaction between Cd3(PW12O40)2 and Na2S, composite CdS nanoparticles with heteropolyanions of PW12O40 3− as balance charge (named as CdS/PW12O40 3−) were synthesized. The electron conductivity behavior of the compound was similar to a strong electrolyte in solution. A salt-like structure was proposed for this kind of nanoparticles.
Keywords: Nanoparticles; CdS; Heteropolyanions; Electrolyte;

Three-nuclear Sn3(μ-OH)2 moieties formed through coordinate dative bonds are associated into chains through Sn⋯Br secondary interactions which are self-assembled in a three-dimensional lattice through OH⋯Br hydrogen bonds.Trinuclear Sn3(μ-OH)2 moieties formed through coordinate dative bonds are associated into chains through secondary Sn⋯Br interactions and further self-assembled in a three-dimensional network through O–H⋯Br hydrogen bonds.

The interaction of Ta2(OMe)10 with Re2O7 in toluene in 1:2 ratio provided an approach to a new bimetallic complex, Ta2(OMe)8(ReO4)2(I), which in its solid state structure and solution behavior displayed a close analogy to the homometallic M2(OMe)10, M=Nb, Ta, and to M2O2(OMe)8, M=Mo, W, complexes.
Keywords: Metal alkoxides; Methoxide; Rhenium complexes; X-ray structure; Solution dynamics;

Synthesis and structure of a high-nuclearity oxomolybdenum(V) complex, [Mo12O28(OC2H5)4(C6H7N)8] by Barbara Modec; Jurij V. Brenčič; Jon Zubieta; Pamela J. Hagrman (537-540).
(PyH)[MoOBr4(H2O)]·2/3PyHBr (PyH+=pyridinium cation, C5H5NH+) yielded upon the solvothermal reaction with ethanol and 4-methylpyridine (4-MePy, C6H7N) a novel oxoethoxomolybdenum(V) cluster, [Mo12O28(OC2H5)4(4-MePy)8] 1. Molybdenum atoms are grouped into six MoV 2 pairs linked by single metal–metal bonds. Three crystallographically independent Mo–Mo distances are 2.5578(14), 2.5981(14) and 2.6489(16) Å.
Keywords: Clusters; Polyoxomolybdates; Alkoxo complexes; Pyridine complexes; Crystal structure;

Hydrothermal synthesis and structure of a bi-capped 1D chain (H2en)3H3O[Mo8V4O36(VO4)(VO)2]·4H2O by Guoyou Luan; Enbo Wang; Zhengbo Han; Yangguang Li (541-543).
The title compound, (H2en)3H3O[Mo8V4O36(VO4)(VO)2]·4H2O, was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. The crystal data: monoclinic, P21/c, a=19.804(4)  A ̊ , b=20.634(4)  A ̊ , c=11.920(2)  A ̊ , β=94.76(3)°. X-ray crystallographic study showed that the crystal structure was constructed by bi-capped α-Keggin fragment {Mo8V7O42} units linked together by V–O–V bonds to a chain.
Keywords: Heteropolymolybdovanadates; 1D Chain; Crystal structure; Hydrothermal synthesis;

A rearrangement of the 10-boron nido/arachno decaboranyl cluster by Jonathan Bould; Udo Dörfler; Mark Thornton-Pett; John D. Kennedy (544-546).
Upon reaction with SMe2, [2,4-Cl2-nido-B10H12] gives [6,9-(SMe2)2-1,7-Cl2-arachno-B10H10] and [1,2,4-Cl3-nido-B10H11] gives [6,9-(SMe2)2-1,3,7-Cl3-arachno-B10H9], demonstrating a previously unsuspected fundamental rearrangement for the 10-boron arachno/nido cluster type.
Keywords: Borane cluster; 10-Vertex cluster rearrangement; X-ray structure; NMR spectroscopy;

Synthesis and crystal structure of the first cerium sandwich complex of a carborane ligand system by Narayan S. Hosmane; Ying Wang; Hongming Zhang; Yinghuai Zhu; John A. Maguire (547-550).
The reaction of closo-exo-Li(TMEDA)-1-Li(TMEDA)-2,3-(SiMe3)2-2,3-C2B4H4 (1) and anhydrous CeCl3, in a molar ratio of 2:1, in dry benzene at 0 °C produced a novel Ce(III) bent-sandwich complex, [Li(TMEDA)2][1-Cl-1-(μ-Cl)-2,2,3,3-(SiMe3)4-5,6-[(μ-H)2Li(TMEDA)]-4,4,5-[(μ-H)3Li(TMEDA)]-1,1-commo-Ce(2,3-C2B4H4)2] (2), as an orange crystalline solid in 91% yield, thus establishing a pattern of reactivity in the formation of lanthanacarboranes.

The tris(vanadyl)-substituted tungstobismutate(III) [(VO)3(BiW9O33)2]12− anion has been synthesized by reaction of α-B[BiW9O33]9− with VOSO4 in aqueous solution. The anion is made of two α-B[BiW9O33]9− units linked by a belt of three exterior VO2+ groups into an assembly of virtual D3h symmetry. The three vanadium centers are well separated by a V⋯V distance of 5.375(4)–5.474(4) Å.
Keywords: Crystal structure; Tris(vanadyl)-substituted tungstobismutate(III); α-B tungstobismutate; V/W/Bi-mixed polyanion;

Hydrothermal synthesis and characterization of an ammoniumtitanium(IV) phosphate with pyrochlore-type structure by Santiago Garcı́a-Granda; Miguel A. Salvadó; Pilar Pertierra; Anatoly I. Bortun; Sergei A. Khainakov; Camino Trobajo; Aránzazu Espina; José R. Garcı́a (555-557).
A novel titanium(IV) phosphate, (NH4)0.79(P1.14Ti0.86)O3.93(OH)2.07, has been prepared using hydrothermal synthesis with H3PO3, TiCl4, H2O2 and (NH2)2CO; powder X-ray structure determination reveals the P(V) as hexa-coordinated.
Keywords: Phosphorus compounds; Titanium compounds; Pyrochlore structure;

Crystal structure and magnetic properties of a Cu4O4 cubane complex with N-(2-hydroxybenzyl)-propanolamine by Yongshu Xie; Weiming Bu; Xiaolong Xu; Hui Jiang; Qingliang Liu; Yi Xue; Yuguo Fan (558-560).
The crystal structure of [Cu(L 1)]4( 1 ) (H2L1=N-(2-hydroxybenzyl)-propanolamine) contains a Cu4O4 cubane core, involving four intramolecular hydrogen bonds. Magnetic studies reveal a good linear correlation between 2J and the bridge angle φ; the more antiferromagnetic trend than the literature correlations for the alkoxo-bridged complexes is ascribed to the additional superexchange pathways via the multiple hydrogen bonds.
Keywords: Crystal structures; Copper(II) complexes; Magnetic properties; Hydrogen bonds;

Hydrothermal synthesis of two new zinc coordination polymers with mixed ligands by Chuan-De Wu; Can-Zhong Lu; Ding-Ming Wu; Hong-Hui Zhuang; Jin-Shun Huang (561-564).
GraphicThe hydrothermal reactions of zinc acetate with 1,2,4,5-benzenetetracarboxylic anhydride (btc) and 4,4-bipyridine (4,4-bpy) for [Zn2(4,4-bpy)(btc)(H2O)2] n ·2nH2O (1) or imidazole (imi) for [Zn2(imi)4(btc)(H2O)2] n (2) in the molar ratio of 1:1:1:2000 at 170 °C for five days led to the formation of colorless crystals of 1 and 2. The btc ligand acts as a four-dentate bridging ligand in both compounds to link up zinc atoms into linear chain architectures. In 1, the linear chain subpolymers are further interlinked into a lamellar framework via 4,4-bpy ligands. Finally, both 1 and 2 are extended into three-dimensional framework via hydrogen bonding.
Keywords: Hydrothermal synthesis; Coordination material; Zinc compound; Mixed ligands;

Synthesis and characterization of Ba2Be2B2O7 by Hua Qi; Chuangtian Chen (565-567).
Polycrystalline barium beryllium borate, Ba2Be2B2O7, has been synthesized by the solid-state reaction method. Element analyses gave the atomic ratio of Ba:Be:B to be 2:2.11:1.92 in this compound. Scanning electron microscopic results revealed that the synthesized Ba2Be2B2O7 contained irregular grain morphology with an average size of 10  μm . Ba2Be2B2O7 powders were found to exhibit intense second harmonic generation. The suitable formation condition of the high purity Ba2Be2B2O7 is also established.
Keywords: Borate; Synthesis; Ba2Be2B2O7; Second harmonic generation;

A simple solution-based approach for the incorporation of Keggin anions in thin films of octadecylamine (ODA) is described in this paper. The two-step process comprises thermal evaporation of octadecylamine molecules onto solid supports and thereafter immersion of the cationic lipid film into phosphotungstic acid solution. The immersion cycle leads to incorporation of the (PW12O40)3− anions in the lipid film through attractive electrostatic interaction with the protonated amine groups of the octadecylamine molecules in the film. The formation of the octadecylamine-Keggin anion complex results in lamellar ordering of the film.
Keywords: Keggin anions; Lipid films; Electrostatic interaction; Catalytic applications;

The electrospray ionisation mass spectrum of [Ru4(η 6-C6H6)4(OH)4]4+ shows that the main species present in aqueous solution are based on the intact cubane tetramer and the dimer [Ru2(η 6-C6H6)2(OH)2]2+. The latter species is an active benzene hydrogenation catalyst.
Keywords: Ruthenium; Cubane; Electrospray mass spectrometry; Benzene hydrogenation; Catalysis;

The first octanuclear tin(IV)–oxosulfide cluster by Liming Wu; Ling Chen; Jingcao Dai; Chuanpeng Cui; Zhiyong Fu; Xintao Wu (574-576).
The first octanuclear tin(IV)–oxosulfide complex (NH4)2(Et4N)4[Sn8S12O4(SPh)6] has been synthesized by mixing stoichiometric amount of Sn(SPh)4 and (NH4)2WOS3 and thiophenol in DMF. The compound was crystallized in orthorhombic space group Cmcm, Z=4, a=18.0463(4)  A ̊ , b=15.7599(2)  A ̊ , c=19.1914(5)  A ̊ , a single crystal X-ray diffraction analysis revealed two coordinate modes of the tin atoms: five-coordinated distorted rectangular pyramid SnOS4 and six-coordinated octahedron SnO3S3.
Keywords: Tin(IV)–oxosulfide complex; Thiophenol; DMF; Crystal structures;

X-ray crystal structure of [Cd(dpa)2(SCN)2] (dpa=di-2-pyridylamine) is refined in triclinic space group P-1 (no. 2) with a=7.1464(5)  A ̊ , b=9.4368(7)  A ̊ , c=18.5843(7)  A ̊ ,α=77.318(8)°, β=81.487(8)°, γ=71.427(8)° and shows a novel unequivalent coordination of two SCN and a layered structure built by two types of hydrogen bonding and π–π stacking interactions. The luminescence studies show strong blue photoluminescence in range 360–450 nm as a result of the π→π transition on the dpa ligand.
Keywords: Crystal structure; Hydrogen bonds; π–π stacking interactions; Blue luminescence;

Synthesis, characterization and catalytic activity of some organolanthanides in ethylene polymerization by Vitor Lavini; Alessandra de Souza Maia; Ícaro Sampaio Paulino; Ulf Schuchardt; Wanda de Oliveira (582-584).
The synthesis and characterization of a new class of organolanthanide compounds containing the bromide and cyclopentadienyl anions together with a pyrazinamide ligand are presented. The compounds were characterized by elemental analyses, complexometric titration with EDTA, thermal analyses, vibrational spectra in the infrared region. The catalytic activity of these compounds in ethylene polymerization was examined.
Keywords: Organolanthanides; Pyrazinamide; Cyclopentadienyl; Polymerization;

Coordination chemistry of CNH, the simplest isocyanide by Armando J.L. Pombeiro (585-597).
The coordination chemistry of hydrogen isocyanide (CNH), the simplest isocyanide, is presented, comprehending the syntheses of its complexes (by N-protonation of cyanide or trimethylsilyl cyanide derived species, eventually in competition with hydrogen-bond formation), electronic and structural features, hydrogen-bond formation, deprotonation (to give cyanide, isocyanotrifluoroborate or isocyanotriphenylborate species), protonation (to form the aminocarbyne CNH2 species), addition (with epoxides), multicomponent cycloaddition and condensation reactions applied to organic syntheses.
Keywords: Hydrogen isocyanide; Isocyanide; Cyanide; Aminocarbyne; Trimethylsilyl cyanide; Isocyanoborate; Hydrogen-bond; Deprotonation; Protonation; Cycloaddition; Organic synthesis; Electrochemistry;