Inorganic Chemistry Communications (v.7, #5)

Contents List (iii-v).

Interconversion of structurally characterised complexes [PdCl(Se   ̂ N)]2 and [Pd(Se   ̂ N)2]6 with the hemi-labile ligand Se   ̂ N=Me2NCH2CH2CH2Se by Sandip Dey; Vimal K. Jain; Axel Klein; Wolfgang Kaim (601-603).
The homoleptic hexanuclear palladium(II) selenolate [Pd(SeCH2CH2CH2NMe2)2]6 (1) reacts readily with Na2PdCl4 to afford the binuclear [PdCl(SeCH2CH2CH2NMe2)]2 (2) and the latter can be converted back to 1 by treatment with NaSeCH2CH2CH2NMe2. The 1 has a hexagonal cyclo-[PdSe2]6 centre in which two palladium ions are always bridged by two selenolate Se atoms.
Keywords: Palladium; Selenolate ligand; Crystal structure; Hexanuclear complex;

Synthesis and characterization of lead phosphate hydroxyapatite nanoparticles by Zhiliang Xiu; Mengkai Lü; Feng Gu; Shufen Wang; Dong Xu; Duorong Yuan (604-606).
Lead phosphate hydroxyapatite (hereafter PbHA) nanoparticles were prepared with a surfactant-assisted method at different temperatures. It revealed that high temperature was favorable for preparing small size nanoparticles. The function of the surfactant cetyltrimethylammonium bromide (CTAB) had been tentatively presented.
Keywords: Surfactant; Precipitation; Lead phosphate hydroxyapatite; Nanoparticles;

Selected-control synthesis of PbO2 submicrometer-sized hollow spheres and Pb3O4 microtubes by Guangcheng Xi; Yiya Peng; Liqiang Xu; Meng Zhang; Weichao Yu; Yitai Qian (607-610).
Submicrometer-sized PbO2 hollow spheres and Pb3O4 microtubes were prepared by a selected-control synthesis method for the first time. The diameter of the PbO2 hollow spheres is about 200–400 nm and the wall thickness is about 30–50 nm. The Pb3O4 microtubes with tetragonal cross-section are 15–20 μm in length, 3–4 μm in width, and 0.4–0.6 μm in wall thickness. The experimental results indicated that poly(vinyl pyrrolidone) (PVP) plays a unique role in controlling the morphologies of lead oxides.
Keywords: Hollow spheres; Microtubes; Lead oxides; Electrodes;

Syntheses, structures and luminescent properties of four new 1D lanthanide complexes with 2-thiopheneacetic acid ligand by Li-Zhen Cai; Wen-Tong Chen; Ming-Sheng Wang; Guo-Cong Guo; Jin-Shun Huang (611-613).
Four complexes, Ln2(C6H5SO2)6(H2O)3  · 2.25H2O (C6H5SO2 = 2-thiopheneacetic acid, Ln = Ce (1), Pr (2), Nd (3), Sm (4)), have been synthesized with hydrothermal route. The X-ray diffraction analyses reveal that they are characterized by the 1D structure and fluorescence studies show they display interesting luminescent properties in solid state.
Keywords: Crystal structure; Luminescence; Lanthanide; 2-thiopheneacetic acid;

The binding constants of [Ni(L1)]2+ toward alkaline earth metal ions are relatively small compared with those of free 18-crown-6 and those of [Ni(L1)]2+ toward the alkali metal ions. The reduction potential of the [Ni(L1)](ClO4)2 in the presence of alkaline earth metal ions shifts to the positive direction in the order Mg2+  < Ca2+  < Sr2+ and K red/K ox value of this redox process is increased in the order Li+  < Na+  < K+  < Mg2+  < Ca2+  < Sr2+.
Keywords: Binding properties; Electrochemical behaviour; Ni(II) complex; Pendant arm; Crown ether; Redox-switching;

Photocatalytic reactivity of noble metal-loaded ETS-4 zeolites by Guoqing Guan; Tetsuya Kida; Katsuki Kusakabe; Kunio Kimura; Eiichi Abe; Akira Yoshida (618-620).
Noble metal (Pt and Au) loaded ETS-4 zeolites showed stable photocatalytic activity for H2 evolution from water containing CH3OH under UV light irradiation (λ>300 nm), while an original ETS-4 zeolite showed poor photocatalytic activity.
Keywords: Zeolite; Photocatalysis; ETS-4; Hydrogen evolution;

A novel non-planar macrocyclic ligand (5,14-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine)-containing one-dimensional polymer of germanium complex is synthesized for the first time under mild conditions. Its single-crystal X-ray structure is determined. This is the first structural example of macrocyclic ligand-containing one-dimensional polymers.
Keywords: Non-planar macrocyclic ligand; One-dimensional polymer; Germanium complex; Crystal structure;

Electrospun nanofibers of NiO/ZnO composite by Changlu Shao; Xinghua Yang; Hongyu Guan; Yichun Liu; Jian Gong (625-627).
For the first time, nanofibers of PVA/nickel acetate/zinc acetate composite were prepared by using sol–gel processing and electrospinning technique. By high temperature calcinations of the above precursor fibers, nanofibers of NiO/ZnO composite with diameters of 50–150 nm could be successfully obtained. The fibers were characterized by TG/DTA, IR, XRD and SEM. The results showed that the crystallinity and the morphology of the fibers were largely influenced by the calcination temperature.
Keywords: Nanofibers; NiO/ZnO composite; PVA/nickel acetate/zinc acetate composite; Electrospinning; PVA;

Preparation of porous spherical CuI nanoparticles by Ming Yang; Jin-Zhong Xu; Shu Xu; Jun-Jie Zhu; Hong-Yuan Chen (628-630).
Porous spherical CuI nanoparticles with an average diameter of 0.3–0.6 μm have been prepared by a simple reaction between CuO suspension, NH2OH · HCl and KI in the presence of deionized gelatin at room temperature.
Keywords: CuI; Nanoparticles; Porous; Spheres;

Peroxovanadium(V) complexes of α-hydroxyhippuric acid (α-H2hhip), M 2[V2O2(O2)2(α-hhip)2] ·  nH2O [M=NMe 4 + (1), NPr 4 + (2); n=0.5, 5], have been prepared and characterized by elemental analysis and by IR and Raman spectroscopies. The X-ray crystal structure of 2 has been determined as the first crystal structure of an α-hydroxyhippurato complex. A single crystal X-ray diffraction study has shown that the α-hhip ligand behaves as a tridentate chelator adopting the (O, COO, CO) donor set. The coordination geometry of the vanadium atom is a distorted pentagonal bipyramid.
Keywords: Peroxovanadium complexes; α-hydroxyhippuric acid; IR and Raman spectroscopies; Crystal structure;

A novel 3D Nd(III)–Bi(III) coordination polymer generated from EDTA ligand by Vitalie Stavila; Aurelian Gulea; Nelea Popa; Sergiu Shova; André Merbach; Yurii A Simonov; Janusz Lipkowski (634-637).
Novel 3D coordination polymer {NdBi(EDTA)(NO3)2(H2O)7,22} 1 with unprecedented type of coordination of EDTA ligand has been synthesised. It represents the first structurally characterised heterometallic lanthanide–bismuth polyaminocarboxylate and the first example of the Bi(EDTA) moiety with coordinated NO3 anions. One of the two NO3 anions is disordered in two resolvable positions with the 0.74:0.26 occupancy factors. The major component can be formulated as [(H2O)5Nd(μ4-EDTA)Bi(NO3)2] · 3H2O (1a), while the minor component can be described by [(NO3)(H2O)3Nd(μ4-EDTA)Bi(NO3)] · 2H2O (1b).
Keywords: Bismuth(III); Neodymium(III); EDTA; Heterometallic complex; Crystal structure;

The hydrothermal reaction of cyclobutane-1,2,3,4-tetracarboxylic acid (H4CBTC) with Cd(NO3)2  · 4H2O yields the first CBTC containing metal coordination polymer with three-dimensional framework [Cd2(CBTC)(H2O)2] n (1), which is characterized by single-crystal X-ray diffraction analysis, IR spectroscopy and TG analysis.
Keywords: Cyclobutane-1,2,3,4-tetracarboxylate; Cd(II) polymer; 3D framework; Crystal structure; Hydrothermal synthesis;

Room temperature route to phosphorus nitride hollow spheres by Luyang Chen; Yunle Gu; Liang Shi; Zeheng Yang; Jianhua Ma; Yitai Qian (643-645).
Amorphous phosphorus nitride (P3N5) hollow spheres were synthesized via reacting PCl3 with NaNH2 at room temperature. Transmission electron microscopy (TEM) images showed the hollow spheres with a diameter of 80–150 nm. X-ray photoelectron spectra (XPS) were used to determine the molar ratio of 1:1.60 for P:N. The optical properties of the as-prepared P3N5 were investigated.
Keywords: Phosphorus nitride; X-ray powder diffraction; Chemical synthesis;

Spectroscopic and electrochemical characterizations of ferrocene- and biferrocene-functionalized terpyridine octanethiolate monolayer protected clusters were reported. The electrochemical data reveals that there is an interaction between redox centers.
Keywords: Gold cluster; Biferrocene; Terpyridine; Surface plasmon;

The complex [(η-C5Me5)RhIII(η-C7H7)]3+ is characterized by a C5Me5  → C7H7 + ligand-to-ligand charge transfer transition which appears at λ max=340 nm in absorption and 596 nm in emission.
Keywords: Electronic spectra; Photoluminescence; Charge transfer; Rhodium;

A stable, coordinatively unsaturated, 16-electron ruthenium complex bearing P(OH)2(OMe) has been synthesized and characterized. It reacts with H2 resulting in a highly acidic dihydrogen complex.
Keywords: Acidity; Dihydrogen complex; Hydride complex; Diphosphine; Phosphite; Ruthenium;

Stereogenic properties of 1,3-disubstituted derivatives of cyclotriphosphazene: cis (meso) and trans (racemic) isomers by Simon J. Coles; David B. Davies; Robert J. Eaton; Michael B. Hursthouse; Adem Kılıç; Robert A. Shaw; Şule Şahin; Aylin Uslu; Serkan Yeşilot (657-661).
The di-spiro derivatives of the reaction of cyclotriphosphazene with either 3-amino-1-propanol or N-methylethanolamine are expected to exist as cis and trans geometric isomers and be meso and racemic, respectively. The isomers were separated by column chromatography on silica gel and analysed by elemental analysis, mass spectrometry, and 31P and 1H NMR spectroscopies. X-ray crystallography was used to characterise both the cis and trans isomers of the N-methylethanolamino di-spiro derivatives and the cis isomer of the propanolamino di-spiro derivative but, due to a mirror plane for the trans isomer, it was not possible to determine uniquely the NH and O positions and, hence, the cis or trans configuration of the compound. The stereogenic properties of all the compounds were investigated by 31P NMR spectroscopy on addition of a chiral solvating agent (CSA), (S)-(+)-2,2,2-trifluoro-1-(9-anthryl)ethanol. The CSA results confirm that both cis isomers are meso and the trans isomer of the N-methylethanolamino di-spiro derivative is a racemate, as expected. It was also shown that the second isomer of the propanolamino di-spiro derivative was a racemate, confirming that it is the trans isomer and, hence, confirming the original predictions of the stereogenicity of the 1,3-disubstituted cyclotriphosphazenes.
Keywords: Stereogenicity; Crystal structures; cis-1,3-cyclotriphosphazenes; trans-1,3-cyclotriphosphazenes; NMR; CSA (chiral solvating agent);

Solvothermal reaction of Mn(OAc)2  · 4H2O with 4,5-dicarboxyimidazole and phenanthroline resulted in a complex [Mn(phen)(Hdcbi)] n 1 in which Hdcbi as a μ2-bridge links two neighboring manganese(II) ions in chelating mode, forming one-dimensional zigzag chain framework. The fitting of magnetic data (J=−0.11 cm−1, zJ =−0.06 cm−1, g=2.01) indicates weak antiferromagnetic coupling interactions between the Mn(II) sites.
Keywords: Solvothermal synthesis; Manganese complex; One-dimensional chain; Crystal structure; 4,5-dicarboxyimidazole;

The amorphous trivalent chromium hydroxide Cr(OH)3 microspheres and the crystalline Cr2O3 microspheres are prepared on a large scale. And their structure, morphology and properties are well characterized.
Keywords: Hydrothermal reduction; Acryl-amide; Cr(III) oxide microspheres;

Syntheses, structures and magnetic properties of two novel 3D helical dicyanamide complexes containing polyamine ligand by Jun Luo; Xi-Geng Zhou; Song Gao; Lin-Hong Weng; Ze-Huai Shao; Chun-Mei Zhang; Yan-Rong Li; Jie Zhang; Rui-Fang Cai (669-672).
Two isomorphous novel 3D helical dicyanamide complexes, Co(tmeda)(dca)2 (1) and Ni(tmeda)(dca)2 (2) (tmeda=tetramethylethylenediamine) have been synthesized and their crystal structures, IR spectra, magnetic properties were determined. Complex 1 displays antiferromagnetic coupling (T>70 K, θ=−27 K, C=3.78 cm3 mol−1 K) between the adjacent cobalt(II) ions, while weak ferromagnetic interaction (θ=3.8 K, C=1.12 cm3 mol−1 K) is observed in complex 2.
Keywords: Dicyanamide; 3D helical complexes; Coordination polymers; Polyamine; Crystal structures; Magnetic properties;

The conversion of CdO to laminar wurtzite CdSe nanocrystals was achieved in a mixture of ethylenediamine and hydrazine hydrate at room temperature. The mechanism of reaction and the formation of laminar structure were discussed, and it was found that the mixed solvent played a crucial role in conversion.
Keywords: Nanocrystals; Cadmium selenide; Wurtzite; Laminar structure;

The `solid–solid' reaction between Mn(CO)4(PPh3)Br and solid phosphines at temperatures lower than the reactant melting points is shown to occur in the melt.
Keywords: Solid-state reactions; Melt reactions; Manganese; CO substitution;

Ruthenium doped TiO2 fibers by electrospinning by P. Viswanathamurthi; N. Bhattarai; C.K. Kim; H.Y. Kim; D.R. Lee (679-682).
Nano to sub-micron fibers of ruthenium doped titanium dioxide/poly(vinylacetate) hybrid have been prepared by electrospinning method. Pure ceramic metal oxide fibers were obtained by high temperature calcination of the organic–inorganic hybrid fibers. It is observed that the surface morphology and crystallinity of the fibers depend on the calcination temperature and ruthenium content.
Keywords: Sol–gel; Electrospinning; Calcinations; Metal oxide fibers;

A novel 3D nickel twofold-interpenetrating framework with mixed ligand, [Ni3(H2O)6(4,4-bipy)4(SIPA)2] · 8H2O (1), has been hydrothermally prepared. X-ray diffraction shows the 3D framework contains Ni-4,4-bipy 1D chain and 2D bilayer motifs and carboxylate spacers, and the connection of 1D chain and 2D bilayer motifs by carboxylate ligand results in the formation of the final framework with twofold-interpenetration net.
Keywords: Nickel; Twofold-interpenetrating; Mixed ligand; 2D bilayer motifs;

Towards the development of polynuclear electron reservoirs containing terpyridine metal complexes by Teng-Yuan Dong; Mei-ching Lin; Michael Yen-Nan Chiang (687-690).
The preparations of multinuclear supramolecules assembled from 1,1‴-bis(terpyridyl)biferrocene redox-active subunit with Ru(II) metal centers are described. The appreciable variations detected in the Fe2+/Fe3+ oxidation potentials indicate that there is an interaction between the spacer and terminal ferrocenyl moieties. The binuclear bis(terpyridyl)biferrocene appears to be promising bridge which can ensure fast and quantitative transfer of energy within the array.
Keywords: Biferrocene; Metallocene; Electron reservoirs; Supramolecule;

Addition of two equivalents of tris(2-hydroxy-3,5-dimethylbenzyl)amine (H3Lig) to the solution of MoO2(acac)2 in MeOH results in the formation of anionic complex, which precipitates as LigH4[MoO2Lig], a yellow crystalline solid. Crystal structure determinations reveal that the asymmetric unit consists of one [MoO2Lig] anion, one H4Lig+ cation and two molecules of solvent. Three phenoxide groups of the tetradentate ligand are bonded to cis-MoO2 2+-ion in xy-plane, while the amino nitrogen atom completes the distorted octahedral coordination.
Keywords: Molybdenum complex; Phenoxide complex; Crystal structure; Atranes;

The reaction of trans-[Pt](CCPh)2 {[Pt]=(Ph3P)2Pt} (1) with two equivalents of [AgOTf] (2) (OTf=triflate, OSO2CF3) produces polymeric {trans-[Pt][(μ-σ,η2-CCPh)AgOTf]2} n (3) in which [Pt](CCPh)2 fragments are spanned by eight-membered {Ag[μ-OS(O)(CF3)O]}2 cycles. The solid-state structure of 3 is reported. A zigzag chain is set-up by Pt(μ-σ,η2-CCPh)2 and {Ag[μ-OS(O)(CF3)O]}2 units of which the latter moiety is the linking entity.
Keywords: Platinum; Silver; Alkyne; Triflate; Coordination polymer; X-ray;

Square-planar copper (II) complexes of 16-membered hexaaza macrocyclic ligands have been prepared by the one-pot template reactions of formaldehyde and propylenediamine (pn) with alkyl and benzyl amine in the presence of copper (II) ion.
Keywords: Copper complexes; Macrocyclic complexes; Template synthesis; Hexaazacyclohexadecane;

A novel paradigm for metal-induced ring flipping in the copper(II) complex of 1,2-bis(N-methylbenzimidazol-2-yl)benzene triflate by Jayakumar G. Gilbert; Anthony W. Addison; Ponraj Prabakaran; Raymond J. Butcher; Gabriele Bocelli (701-704).
The crystal structures of 1,2-bis(N-methylbenzimidazol-2-yl)benzene (bmbz) 1 and its copper(II) triflate complex 2 have revealed a CuII-induced conformational change in which one of the N-methylbenzimidazole moieties is entirely flipped, as compared to the free ligand, which mimics histidine side-chain flipping in the copper complex of RNase A, and leads to a twisted V-shaped conformation of the ligand in metal complex.
Keywords: Benzimidazole; Copper complex; Conformational change; Metal binding;

A new compound, [NH4]2[Zn(phen)3]2[Zn(phen)2(H2O)2][V16O38(Cl)] · 5H2O (1), was synthesized in the hydrothermal condition. The “naked” [V16O38(Cl)]8− is the first observation with host shell structure in polyoxovanadate chemistry.
Keywords: Hydrothermal synthesis; Crystal structure; Polyoxovanadate; Phen;

Syntheses and structures of homo- and heterobimetallic, chloro-bridged complexes containing the RuCl3(AsPh3) n fragment (n=1, 2) by Sébastien Gauthier; Laurent Quebatte; Rosario Scopelliti; Kay Severin (708-712).
The reaction of [RuCl3(AsPh3)2(MeOH)] with the dimeric complexes [(cod)RhCl]2, [(ppy)RhCl]2 (ppy=cyclometalated 2-phenylpyridine), [(cymene)RuCl2]2 and [Cp*MCl2]2 (M=Rh, Ir) has been investigated. The structure of the resulting products was shown to depend on the reaction partner. Whereas for the rhodium complexes [(cod)RhCl]2 and [(ppy)RhCl]2, heterobimetallic compounds with two halogeno-bridges were found, the reactions with the halfsandwich complexes [(cymene)RuCl2]2 and [Cp*MCl2]2 gave triply bridged products with concomitant formation of mononuclear [(π-ligand)MCl2(AsPh3)] side products. The new complexes were all characterized by single crystal X-ray analysis.
Keywords: Heterobimetallic complex; Organometallic complex; Ruthenium; Rhodium; Iridium;