Inorganic Chemistry Communications (v.5, #6)

Contents List (iii-iv).

Crystal structure of tetraphenyldiboroxane a monomer diboroxane by Thomas Lange; Uwe Böhme; Gerhard Roewer (377-379).
Commonly known syntheses of triphenylborane lead to products of varying purity. Because of by-products, the individual batches of triphenylborane samples have different reactivity and leading to different reaction products. Tetraphenyldiboroxane as the main by-product of the BPh3 synthesis was isolated and characterized by means of 11B-NMR and X-ray structure analysis.
Keywords: Boron compounds; Diboroxanes; Tetraphenyldiboroxane; Crystal structure;

Synthesis, structural diversity, inter-conversion and reactivity of Cu(II) complexes of hydroxy-rich molecules by Mishtu Dey; Chebrolu P. Rao; Pauli K. Saarenketo; Kari Rissanen (380-383).
Tetranuclear Cu(II) complexes having linear, cubane and pseudodouble-cubane cores were synthesized using hydroxy-rich molecules possessing amine and imine groups. The products were structurally characterized and were studied for their ability to oxidize catechol as well as for their inter-conversion between mono- and tetra-nuclear complexes.
Keywords: Tetranuclear cubane core; Pseudodouble-cubane; Inter-conversion; Catechol oxidation by Cu(II) complexes;

Adding one equivalent of H2O2 to compounds of stoichiometry MoCl2(O)2(OPR3)2, OPR3=OPMePh2 or OPPh3, leads to the formation of oxo–peroxo compounds MoCl2(O)(O2)(OPR3)2. The compound MoCl2(O)(O2)(OPMePh2)2 crystallized with an unequal disorder, 63%:37%, between the oxo and peroxo ligands and can be isolated in reasonable yields. MoCl2(O)(O2)(OPPh3)2 was not isolated in pure form, co-crystallized with MoCl2(O)2(OPPh3)2 in two ratios, 18%:82% and 12%:88%, respectively, and did not contain any disorder in the arrangement of the oxo and peroxo groups. These complexes accomplish the isomerization of various allylic alcohols at rates competitive to that reported for CH3ReO3.
Keywords: Catalysis; Isomerization; Molybdenum oxo–peroxo compounds; 18O isotopic studies;

Potassium tungstate(VI) reacts with nitrilotriacetic acid in water to form tripotassium hydrogen oxo-μ-bis[trans-nitrilotriacetato-cis-dioxotungstate(VI)] dihydrate. The octahedrally coordinated tungsten atom is N,O,O-chelated by the nitrilotriacetate entity, which is linked by its acid hydrogen [O⋯O=2.54(2) Å] to form a chain that propagates along a diagonal of the bc face of the monoclinic unit cell.
Keywords: Dioxotungstate(VI); Tungsten; Nitrilotriacetic acid; Crystal structure;

The complex (phanephos)ReI(CO)3Cl with phanephos=4,12-bis(diphenylphosphino)-[2.2]-paracyclophane is characterized by a lowest-energy intraligand (IL) excited state of the 2,2-paracyclophane moiety. This IL transition appears at λ max =340  nm in absorption and at 383 (fluorescence) and 480 nm (phosphorescence, at r.t.) in emission.
Keywords: Electronic spectra; Luminescence; Rhenium complexes; Cyclophane;

Spontaneous magnetization in [1-(4-cyanobenzyl)pyridinium][Pt(mnt)2]: synthesis, crystal structure and magnetic property by Jingli Xie; Xiaoming Ren; You Song; Wenjun Tong; Changsheng Lu; Yuangen Yao; Qingjin Meng (395-398).
A new complex [1-(4-cyanobenzyl)pyridinium][Pt(mnt)2] (1), in which mnt2−  = maleonitriledithiolate, has been prepared and characterized. In the solid state, anions and cations of 1 form completely segregated stacking column, and the [Pt(mnt)2] anion column behaves as one-dimensional (1-D) spaced magnetic chains. 1 spontaneously magnetizes at low temperature, which may arises from spin canting.
Keywords: Maleonitriledithiolate; Crystal structure; Magnetic property; Spin canting;

Hydrothermal synthesis and characterization of nanorods “Li x V2−δ O4−δ ·H2O” by Hai Tao Zhang; Zhou Gui; Rong Fan; Xian Hui Chen (399-402).
Nanorods “Li x V2−δ O4−δ ·H2O” were hydrothermally synthesized with starting agents LiOH·H2O and V2O5, and reducing agent hydrazine monohydrate (NH2NH2·H2O) under alkaline condition at 160 °C. The samples were characterizated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The nanorods obtained have diameters from 80 to 100 nm with length up to several micrometers. Molecular coordination and assembly mechanism can be assumed to explain the formation of one-dimensional nanorods.
Keywords: Hydrothermal synthesis; Li x V2 - δ O4 - δ ·H2O; Nanorods; Vanadium oxide;

Unexpected assembly of a tetranuclear copper(II) complex bridged by glyoximate groups by Chun-Hui Li; Ru-Ji Wang; Hui-Zhong Kou; Ya-Dong Li (403-406).
The tetranuclear copper(II) complex of composition [Cu4(dmg)2(Hdmg)2(H2dmg)2(H2O)3](ClO4)2·3H2O (H2dmg=dimethylglyoxime) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. The structure consists of one Hdmg/dmg2−-bridged tetranuclear cation [Cu4(dmg)2(Hdmg)2(H2dmg)2(H2O)3]2+, two uncoordinated perchlorate anions and three crystallization water molecules. The tetranuclear cation can be described as two Hdmg/dmg2−-bridged dimers: {[Cu(dmg)(Hdmg)(H2O)][Cu(H2dmg)(H2O)]}+ and {[Cu(dmg)(Hdmg)][Cu(H 2 dmg  )(H 2 O)]}+ , which are linked through the oxime group (Hdmg) of the former dimer. The H2dmg ligands in the cation co-ordinate to the copper ion as capping ligands. The geometry around each copper atom is a distorted square pyramid. The IR and UV–Vis spectra have been investigated.
Keywords: Copper complexes; Tetranuclear complexes; Oximato-bridge; Crystal structures;

Aqueous ammonia route to Cu1.8S with triangular and rod-like shapes by Yuanfang Liu; Jinbo Cao; Yuanyuan Wang; Jinghui Zeng; Yitai Qian (407-410).
Digenite crystalline Cu1.8S was synthesized through solvothermal reaction of CuCl2·2H2O and sulfur powder at low temperature in aqueous ammonia. X-ray powder diffraction (XRD) pattern indicates Cu1.8S is cubic phase. Transmission electron microscope (TEM) shows Cu1.8S obtained at 160 °C is triangular and Cu1.8S formed at 140 °C is rod-like. X-ray photoelectron spectrum (XPS) was used to determine the composition of as prepared products. The influence of solvent and reaction temperature was investigated. Raman spectrum of Cu1.8S was recorded.
Keywords: Cu1.8S; Triangular; Rod-like; Aqueous ammonia route;

Synthesis and spectroscopic properties of anhydrotetracyclineplatinum(II)dichloride by Aref A.M Aly; Andreas Strasser; Arnd Vogler (411-413).
The reaction of tetracycline with K2PtCl4 in glacial acetic acid leads to the dehydration of tetracycline to anhydrotetracycline (ahtc) which coordinates as a bidentate ligand to the PtCl2 moiety. The composition of Pt(ahtc)Cl2 is confirmed by elemental analysis and mass spectrometry. On the basis of the electronic spectra it is suggested that the coordination takes place at the A ring of ahtc while the BCD ring system is preserved as separate chromophore. It is characterized by a long-wavelength absorption and fluorescence which appear at λ max=428 and 550 nm, respectively, for the free ahtc ligand and λ max=425 and 550 nm for Pt(ahtc)Cl2.
Keywords: Electronic spectra; Luminescence; Platinum; Tetracycline;

Ru4(μ-CO)(CO)944-C6H4)(η214-PPhCH2CH2PPh2): an unusual pyrolysis product of Ru3(CO)10(dppe) containing a benzyne ligand by Enrique Lozano Diz; Antonia Neels; Helen Stoeckli-Evans; Georg Süss-Fink (414-417).
The thermal decomposition of Ru3(CO)10(dppe) in refluxing benzene gives, in contrast to the pyrolysis of the dppm analogue, the tetranuclear cluster Ru4(μ-CO)(CO)944-C6H4)(η214-PCH2CH2PPh2) (1) along with Ru3(CO)9212-C6H5)(η312-PPhCH2CH2PPh2) (2). The single-crystal structure analysis of 1 reveals a square-planar tetraruthenium skeleton containing a η44-benzyne ligand as well as a η214-phosphinidene–phosphine ligand.
Keywords: Ruthenium; Pyrolysis; Cluster; Benzyne; Carbonyl; Phosphinidene–phosphine;

Synthesis, structure and properties of a new unsymmetric tetranuclear mixed-valence vanadium(IV/V) complex containing distinct V2O3 3+ cores by Ademir Neves; Liane M. Rossi; Adailton J. Bortoluzzi; Antônio S. Mangrich; Wolfgang Haase; Otaciro R. Nascimento (418-421).
The synthesis, X-ray crystal structure, spectroscopic, and electrochemical properties of a new tetranuclear vanadium(IV,V,IV,V) complex [(VO)4(btppnol)2(μ-O)2](ClO 4)2·2DMF·2H 2 O  ( 1 ) utilizing the previously described unsymmetrical dinucleating ligand N-(2-hydroxybenzyl)-N,N ,N -tris(2-pyridylmethyl)-1,3-diaminopropan-2-ol (H2btppnol) are reported. The complex comprises two different [V2O3]3+ core structures: one [V2O3]3+ core in a syn-dioxo-μ-O(alkoxo) configurarion and another [V2O3]3+ core in an anti-dioxo-μ-oxo configuration, as well as being composed of non-equivalent vanadium centers as a consequence of the use of an unsymmetrical ligand. This complex represents the first example in the literature of a vanadium complex with this particular structure and its interesting electrochemical and spectroscopic properties were investigated.
Keywords: Crystal structure; Unsymmetric tetranuclear vanadium(IV/V) complex; Electrochemistry; EPR;

New macrobicyclic tricompartmental ligands and their mononuclear copper(II) complexes of type [CuH2L](ClO4)2 have been synthesized from the precursor compound 3,4:10,11-dibenzo-1,13[N,N {bis(3-formyl-2-hydroxy-5-methyl)benzyl}diaza]-5,9-dioxa-cycloheptadecane with diamines like en, pn and bn by template method. These complexes have been characterized by IR, UV spectral and X-ray studies. Complex [CuH2L3](ClO4)2 (in L3 the diamine used is bn) crystallized as triclinic system with space group p-1. The crystal structure explains that the geometry around copper is distorted square planar. Among the three compartments, it is interesting to observe that the metal ion prefers to be encompassed by the compartment containing phenolic oxygens and imine nitrogens (N2O2). From X-ray studies the presence of perchlorate anions, acetonitrile solvent molecules and the protonation of tertiary nitrogen atoms were well understood. All the complexes show hyperfine splittings in ESR spectra. The μ eff values observed in the range 1.69–1.72 BM are close to the spin only value of single copper(II) ion. Cyclic voltammetry studies of these complexes depict one electron quasireversible reduction in the range −0.80 to −0.90 V at negative potential. A red shift in UV–Visible spectra and shifting of reduction potential towards anodic in cyclic voltammetry were witnessing the distortion of the geometry around metal center from the planarity as the macrocyclic chain length in imine nitrogen compartment increases.
Keywords: Copper(II) complexes; Macrobicyclic ligands; Crystal structure; Electrochemistry;

A new girdle-like polyoxomolybdate was synthesized and characterized by single crystal X-ray diffraction. Study on its hollow central hole indicates that it is some kind of “inorganic crown ether” and can act as the host of some cations.
Keywords: Polyoxomolybdate; Crystal structure; Girdle-like structure; Inorganic crown ether; Host–guest chemistry;

Unprecedented phosphino copper(I) derivatives of tris(pyrazolyl)methanesulfonate ligand co-ordinated to metal in an unusual κ3-N,N,O fashion by Carlo Santini; Maura Pellei; Giancarlo Gioia Lobbia; Augusto Cingolani; Riccardo Spagna; Mercedes Camalli (430-433).
New copper(I) triorganophosphine derivatives [Cu(R3P)(Tpms)] have been synthesised from the reaction of CuCl with PR3 (R = phenyl or p-tolyl) and lithium tris(pyrazolyl)methanesulfonate (Tpms). The complexes obtained have been characterised by elemental analyses and FT-IR in the solid state and by NMR ( 1 H and 31 P{1 H}) spectroscopy and conductivity measurements in solution. Single crystal structural characterisations were undertaken for [Cu(Ph3P)(Tpms)] which is the first example of structurally characterised complex containing the [Tpms] ligand co-ordinated to a metal ion in an unusual κ3-N,N,O fashion.
Keywords: Copper(I) complexes; Tris(pyrazolyl)methanesulfonate ligand; Crystal structure;

Synthesis, structure and catalase-like activity of a new dinuclear mixed valence MnIIMnIII complex containing an unsymmetric N5O2 donor ligand by Peter Karsten; Ademir Neves; Adailton J. Bortoluzzi; Joachim Strähle; Cecilia Maichle-Mössmer (434-438).
The new dinuclear mixed valence [MnIIMnIII(BPBPMP)(OAc)2]BF4 complex with the unsymmetrical polydentate ligand 2-bis[{(2-pyridylmethyl)-aminomethyl}-6-{(2-hydroxybenzyl)(2-pyridylmethyl)}-aminomethyl]-4-methylphenol (H2BPBPMP) was synthesized. The complex has an MnIIMnIII(μ-phenoxo)(μ-OAc)2 core and was structurally, IR and UV–Vis spectroscopically and by cyclic voltammetry characterized. The reactivity towards H2O2 shows a catalase-like activity.
Keywords: Crystal structure; Dinuclear MnIIMnIII complex; Mixed valence; Unsymmetric ligand; Catalase-like activity; Cyclic voltammetry;

Heterobimetallic lithium organoaluminum and organogallium complexes: potential single precursors for MOCVD of LiMO2 thin films by Eunhee Jung; Seung H Yoo; Taek-Mo Chung; Chang G Kim; Yunsoo Kim; Duk Young Jung (439-441).
The reaction of Me2MCl with two equivalents of Li(OCH2CH2OMe) resulted in the formation of dimeric bimetallic complexes, [Li(OCH2CH2OMe)2MMe2]2 {M=Al (1), Ga (2)}. The crystal structures of 1 and 2 are dimeric and contain eight-membered rings that are similar to a beach chair consisting of a plane of four oxygen and two lithium atoms with each aluminum or gallium metal atom above and below this plane. Thermal analysis of 2 indicates that the dimeric complexes are volatile enough to be suitable as potential single precursors for metal organic chemical vapor deposition (MOCVD) of LiMO2 films.
Keywords: Single precursor; MOCVD; LiGaO2; LiAlO2;

The bridging ligand 2,6-bis(diphenylphosphino)pyridine, L, was used to synthesize two palladium complexes: Pd3Cl6(μ-L)3 has a C2 axis passing through an 18-membered macrocyclic ring, in which two cis- and one trans-coordinated palladium(II) atoms are alternately bridged by three L ligands; [Pd2(μ-L)2]2+ exhibits a rare coordination mode in which two metal–metal bonded palladium(I) atoms (Pd–Pd = 2.5525(7) Å) are each P, N-chelated by one ligand and connected to the bridging phosphorus atom of the other ligand.
Keywords: 2,6-Bis(diphenylphosphino)pyridine; Palladium(I); Palladium(II); Metal–metal bond;

Calculations on the [MoO(OPh)(OPMe3)T] (T=hydrotris(1-pyrazolyl)borate) model system show that the calculated OMoOP dihedral angle is in good agreement with the experimental value found in the crystal structure of [MoO(OPh)(OPEt 3)  T 3Pr ] (T3Pr=hydrotris(3-isopropyl-1-pyrazolyl)borate) and very different than the calculated value for the [MoO(SH)2(NH3)2(OPMe3)] model system. This indicates that the types of ligands coordinated to the molybdenum atom are responsible for the value of the dihedral angle and not the crystal packing forces in the crystal structure.
Keywords: Molybdenum; Oxygen transfer reaction; DFT; Ligands;

Tetrakis(pyrazol-1-ylmethyl)methane and its hypodentate binuclear complex with silver(I) nitrate by David A. McMorran; Stephan Pfadenhauer; Peter J. Steel (449-451).
The preparation and X-ray crystal structure of tetrakis(pyrazol-1-ylmethyl)methane are described. This new ligand reacts with silver(I) nitrate to give a M2L2 complex, in which the ligand bridges two trigonal silver atoms with bidentate and monodentate coordination domains. As such the ligand is hypodentate with one non-coordinated pyrazole group.
Keywords: Crystal structure; Silver complex; Polydendate ligand complex; Chelate complex;