Inorganic Chemistry Communications (v.3, #7)

A one-step synthesis of protected functionalised titanocene dichlorides by Margaret A.D McGowan; Patrick C McGowan (337-340).
We report a novel, high yield one-step synthesis of water stable and soluble titanocene dichloride dihydrochloride salts from the direct reaction of the neutral amino-substituted cyclopentadienes with TiCl4. The following novel complexes have been synthesised: C5H4(CH2)2N(CH2)5]2TiCl2 (5), [C5H4CH(CH2)4NMe]2TiCl2 (6), [C5H4(CH2)2N(CH2)5]2TiCl2·2HCl (7), [C5H4CH(CH2)4]2NMeTiCl2·2HCl (8), [C5H4(CH2)2N(CH2)5]2TiMe2 (9).
Keywords: Anti-tumour agents; Cyclopentadienyl; Functionalisd titanocene dichlorides; One step synthesis; Water soluble titanium (IV) complexes;

The triboluminescent and photoluminescent spectra of morpholinium tetrakis(dibenzoylmethide)europate is superimposed, and its triboluminescence exhibits the most brilliantly triboluminescent activity in the complexes previously known. The crystal structural determination reveals that a noncentrosymmetric space group and disorder in the chelate ring correlate well with the observed triboluminescent activity.
Keywords: Triboluminescence; Europate dibenzoylmethide; Morpholinium; Crystal structure;

Unexpected guest-controlled formation of two-layered structure in supramolecular adduct of [W3S4(H2O)9]4+ and cucurbituril by Danil N. Dybtsev; Olga A. Gerasko; Alexander V. Virovets; Maxim N. Sokolov; Vladimir P. Fedin (345-349).
A new supramolecular adduct {[W3S4(H2O)8Cl][(PyH⊂C36H36N24O12)]}Cl4·15.5H2O (1·15.5H2O) was obtained when pyridine was added to the reaction mixture of cucurbituril and [W3S4(H2O)9]4+ in 3 M HCl. X-ray crystal structure analysis of 1·15.5H2O revealed layered motive of the structure with two different types of cucurbituril molecules. A PyH+ molecule is encapsulated in the cavity of each of the cucurbituril molecule. Under vacuum it loses 13.5 H2O molecules and gives {[W3S4(H2O)8Cl][(PyH⊂C36H36N24O12)]}Cl4·2H2O (1·2H2O).
Keywords: Sulfide clusters; Tungsten; Cucurbituril; Supramolecular adducts; Inclusion compounds; Crystal structures;

Beryllium complexes with mono- and tripodal- phosphinoxide ligands. X-ray crystal structure of [{N(CH2PPh2O)3}Be(OH2)](ClO4)2 by Franco Cecconi; Carlo A. Ghilardi; Stefano Midollini; Annabella Orlandini (350-353).
The ligands triphenylphosphinoxide, tris(2-diphenylphosphorylmethyl)amine and tris(2-diphenylphosphorylethyl)amine have been found to displace the coordinated water molecules from the [Be(H2O)4]2+ cation, in quite mild conditions, to give respectively the complexes [Be(OPPh3)4](ClO4)2, 1, [(N(CH2PPh2O)3)Be(OH2)](ClO4)2, 2 and [(N(CH2CH2PPh2O)3)Be(OH2)](ClO4)2, 3. The compounds have been characterized through NMR spectroscopy and X-ray crystallography. Complex 2 is the first beryllium complex with a ligand containing the phosphoryl function, whose molecular structure has been determined by an X-ray diffraction study.
Keywords: Beryllium complexes; Phosphinoxide complexes; 9Be NMR; X-ray crystal structure;

Highly diastereoselective cyclopalladation of α-ferrocenylethylphosphine: X-ray study of the first phosphapalladacycle of planar chirality by Valery V Dunina; Ol'ga N Gorunova; Michail V Livantsov; Yuri K Grishin; Lyudmila G Kuz'mina; Nadezhda A Kataeva; Andrei V Churakov (354-357).
First planar chiral phosphapalladacycle was prepared in diastereomerically pure state via direct cyclopalladation of the di-tert-butyl-1-ferrocenylethylphosphine. The palladacycle structure was confirmed by 1 H NMR spectra; relative configuration of central and planar chirality was determined by an X-ray diffraction study of the triphenylphosphine adduct.
Keywords: Planar chirality; Phosphapalladacycle; Crystal structures; Conformation; Ferrocenylethylphosphine;

The reaction of (dtbpm-κ2 P)Pd(CH2SiMe3)2 (1) [dtbpm=bis(di-t-butylphosphino)methane] with dimethyl diazomalonate (2) yields dinitrogen and the diphosphinomethanide palladium(II) complex [HC(PtBu2)22 P]Pd[(MeO2C)2CH-κ2 O] (3). Its molecular structure in the solid state was determined by single-crystal X-ray diffraction.
Keywords: Diazoalkane; Palladium; X-ray structure; Ylide;

A novel dimer of oxo-di(acetato)-bridged manganese(III) dimers complex of potential biological significance by Rafael Ruiz; Claudio Sangregorio; Andrea Caneschi; Patrizia Rossi; Ana B Gaspar; Jose A Real; M.Carmen Muñoz (361-367).
Assembly of the tetranuclear oxomanganese(III) acetato cluster [Mn4O2(O2CMe)7(phen)2](BF4) from the dinuclear oxo-di(acetato)-bridged manganese(III) species [Mn2O(O2CMe)2(H2O)2(phen)2](BF4)2·3H2O in aqueous/acetic acid MeOH solution occurs via the new ‘dimer of dimers’ MnIII complex [Mn2O(O2CMe)3(H2O)(phen)2](BF4)·MeOH possesing an unprecedent [Mn4(μ-O)2(μ-O2CMe)4(μ-OH2 O2CMe)2] core.
Keywords: Carboxylato complexes; Cluster compounds; Crystal structures; Manganese; N ligands; O ligands;

Reaction between RhX(PPh3)3 (X = Cl, Br, I) and (η 5-C5H4Me)W(CO)3Y (Y = Cl, Br, I) occurs in both the solution and the solid state and leads to exchange of both CO/PPh3 and X/Y between the two reactants.
Keywords: Solid state reactions; Rhodium; Tungsten; Substitution reaction; Ligand exchange;

Fe(CO)5 appeared to be a good catalyst for competitive silylation of olefins (vinylsilanes, styrene) by vinylsilanes and hydrosilane (e.g. Et3SiH). The catalytic measurements for Fe(CO)5+ Et3SiH system and a stoichiometric study on the insertion of olefin into Fe–Si bond in CpFe(CO)SiMe3 confirm the mechanism of catalysis involving the first reported β-silyl transfer (from carbon of β-silylethyliron) to iron atom accompanied by dehydrogenative silylation of the olefin.
Keywords: Silylative coupling; Iron–silyl-hydride-complexes; Vinylsilanes;

Synthesis and coordination studies of new ferrocene-bridged bis(1,8-naphthyridine) by Rubén Pastene; Hubert Le Bozec; Sergio A Moya (376-378).
The new ferrocene-bridged bis(1,8-naphthyridine) ligand 1 has been prepared in a good yield from 1,1′-diacetylferrocene and 2-aminonicotinoaldehyde. The coordination with copper(I) and silver(I) gives mononuclear complexes, showing that 1 can act as a tetradentate ligand.
Keywords: Naphthyridine complexes; Ferrocene complexes; Copper complexes; Silver complexes;

Ethylenediammonium tritungstate, (C2H10N2)[W3O10], has been hydrothermally synthesized and structurally characterized. The structure of title compound consists of infinite chains running parallel to the b axis, that are made up of distorted WO6 octahedra linked through shared corners and edges. The ethylenediammonium ions occupy interstrand region providing space-filling and charge-compensation to anionic tritungstate matrix.
Keywords: Hydrothermal synthesis; Tungstate; Crystal structures; Polyanions compounds;

The kinetics of the inner intramolecular electron transfer (or self-redox) reactions between two molecules of bis(disubstituted-dithiophosphinato)copper(II) complexes was studied by spectrophotometric stopped-flow technique in ROH/water. It was found that maximal absorption at 420 nm corresponding to the band of the initial complex is obtained at Cu(II)/ligand ratio 1:2. The kinetic runs following the decreasing absorption at 420 nm show that the reaction is second order in respect to CuII(R2-dtph)2 thus confirming the idea of an associate formation between two CuII(R2-dtph)2 molecules. The rate constant of the process strongly depends on the size and shape of the remote R substituents. The lower reaction rate at bulkier substituents is in agreement with the suggestion of hindered formation of the proposed associate. The rate constant also depends on the ROH/water ratio and on the nature of alcohol corresponding to the proposed reaction mechanism.
Keywords: Kinetics and mechanism; Electron transfer; Copper complexes; Dithiophosphinate complexes;

First heterodifunctional ligand derived from a tetradentate phosphine: synthesis and characterization of cis,trans,cis-1,3-bis(diphenylphosphino)-2,4-bis(diphenylphosphinothioyl)cyclobutane and its complex with PdCl2 by Thomas Stampfl; Rainer Haid; Christoph Langes; Werner Oberhauser; Christian Bachmann; Holger Kopacka; Karl-Hans Ongania; Peter Brüggeller (387-392).
Cis,trans,cis-1,2,3,4-tetrakis(diphenylphosphino)cyclobutane (dppcb) can be selectively oxidized by S in toluene to the disulfide cis,trans,cis-1,3-bis(diphenylphosphino)-2,4-bis(diphenylphosphinothioyl)cyclobutane (dppcbS2). DppcbS2 is the first heterodifunctional ligand derived from a tetradentate phosphine obtained with good yield and high purity. It reacts with two equivalents of PdCl2 producing [Pd2Cl4(dppcbS2)] (1). Both dppcbS2 and 1 have been fully characterized by X-ray structure analyses, NMR spectroscopy ( 31 P{ 1 H}, 13 C{ 1 H}, 1 H), FAB mass spectrometry, elemental analyses and melting points. The possible catalytic applications of the versatile heterodifunctional ligand dppcbS2 are discussed in view of the two X-ray structures of dppcbS2 and 1.
Keywords: Crystal structures; Heterodifunctional ligands; Phosphinothioyl ligands; Palladium complexes; Tetradentate phosphines; Catalytic applications;

Equimolar quantities of [ReBr(CO)5] and I2 react in refluxing acetonitrile for 5 h to give the cationic tris(acetonitrile) complex fac-[Re(CO)3(NCMe)3]·BrI2 (1) in a quantitative yield, via the first iodine promoted halide abstraction reaction. The structure of 1 has, as expected, a facial arrangement of carbonyl and acetonitrile ligands, with the linear anion, BrI2 as the counter ion.
Keywords: Iodine-induced halide abstraction; fac-[Re(CO)3(NCMe)3]·BrI2; Crystal structure;

The reaction of cis-[PtCl2(PPh3)2] and NaSePh in benzene produces a mixture of cis- and trans-isomers of the monomeric platinum complex [Pt(SePh)2(PPh3)2]. The low-temperature X-ray structures of both isomers are reported. The structure of cis-[Pt(SePh)2(PPh3)2] is the first crystallographic characterized cis-isomer of mononuclear platinum(II) complex containing only non-chelating organoselenolato and phosphine ligands.
Keywords: Platinum complexes; Selenium complexes; Crystal structures; Phosphorus NMR; Platinum NMR;