A series of M2W2(O)(2)(acac)(2)(OMe)(10) [M = Co (1), Ni (2), Mg (3), Zn (4)] have been synthesised and structurally characterised by X-ray crystallography. All the compounds share common structural features which are identical to the analogous molybdenum species, with four edge-sharing octahedra situated in the same plane, and incorporating two mu(3)-bridging and four mu(2)-bridging methoxide groups. The divalent metal M and tungsten have both octahedral coordination environments with six oxygen atoms. The structure of Na[Zn(acac)(3)] (6), a by-product of a failed synthesis of 4, is also reported, and is a linear polymer in which [Zn(acac)(3)](-) anions use all six oxygen atoms to link sodium cations either side of the anion.Thermal decomposition of representative samples (1, 3) shows them to be single-source precursors for metal tungstates MWO4. When the decomposition is carried out under an autogenerated pressure (RAPET) at 700 degrees C 1 forms CoWO4 nanoparticles, along with WOx-filled carbon nanotubes and amorphous carbon, while 3 forms MgWO4 nanoparticles and rods, though the latter lack a carbon shell and are much shorter in length. (c) 2013 Elsevier Ltd. All rights reserved.

Three novel heterobimetallic W-O-M clusters have been synthesised by the hydrolysis of mixtures of W(O)(OPri)(3)(bdmap) with Ti(OPri)(4), Zn(acac)(2) and Al(OPri)(3), respectively. A fourth, related W-O-Ni cluster has been obtained by adventitious hydrolysis of a mixture of W(O)(OMe)(4) and Ni(dmap)(2) [Hbdmap = 1,3-bis-(dimethylamino)-propan-2-ol; Hdmap = 1-(dimethylamino)propan-2-ol]. W2Ti2(O)(2)(mu(2)-O)(4)(OPri)(6)(mu(2)-bdmap)(2) (1) adopts a central W2Ti2O6 core with an adamantane-like structure while W2Al2(O)(2)(OPri)(2)(mu(2)-O)(4)(mu(2)-bdmap)(4) (3) has an analogous W2Al2O6 core but which adopts an isomeric cube arrangement with two parallel sides missing. W2Zn2(O)(2)(mu(2)-O)(3)(OPri)(2)(acac)(2)(mu(2)-bdmap)(2) (2) is similar to 1 but the two bidentate acac groups result in the elimination of one mu(2)-O bridge; the resulting W2Zn2O6 core forms an adamantane structure with one W-O-Zn linkage missing. In contrast, W4Ni4(O)(4)(OMe)(4)(mu(2)-OMe)(4)(mu(2)-O)(4)(dmap)(8) (4) forms a tetrameric square of four linked W-O-Ni units. (C) 2013 Elsevier Ltd. All rights reserved.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The tungsten aminoalkoxides W(O)(OPr(i))(3)L [L = dmae, OCH(2)CH(2)NMe(2) (1); bdmap, OCH(CH(2)NMe(2))(2) (2); tdmap, OC(CH(2)NMe(2))(3) (3)] have been synthesised. Controlled hydrolysis of 1-3 has allowed isolation of W(4)O(4)(μ-O)(6)(dmae)(4) (4), W(4)O(4)(μ-O)(4)(OPr(i))(4)(bdmap)(4) (5), W(6)O(6)(μ-O)(9)(tdmap)(6) (6), W(4)O(4)(μ-O)(6)(tdmap)(4) (7), W(4)O(4)(μ-O)(6)(tdmap)(4)·4H(2)O (7a), all of which have been characterised by X-ray crystallography. 4, 7, 7a each embody a W(4)O(6) core with adamantane structure, 5 incorporates a folded W(4)O(4) square and 6 has a trigonal prismatic W(6)O(9) at its heart. 7 decomposes in air at to give orthorhombic WO(3), while 1-3 decomposed under an autogenerated pressure (Reaction under Autogenic Pressure at Elevated Temperatures, RAPET) to form mixtures of carbon-coated WO(x) needles and carbon spherules.

Reaction of Li-2[W(NBut)(4)] with two equivalents of SbCl3 at -78 degrees C yields orange-red crystals of the novel heterobimetallic Sb2W(NBut)(mu(2)-NBut)(mu(3)-NBut)(2)Cl-3(mu(2)-Cl) (1) in low yield (25%). From a 1:4 reaction stoichiometry, in addition to 1 crystals of [W(NBu2t)(H2NBut)Cl-2](2). trans-[Sb(Cl)(mu-NBut)](2) (2), [W(NBu2t)(H2NBut)Cl-2](2)center dot SbCl3 (4), Sb2W3Cl7(mu(2)-O)(mu 3-O)(2)(NBu2r)(3)(NHBut)(mu(2)-NBut)(2) (3) and Sb2W(NBut)(mu(2)-NBut)(mu(3)-NBut)(2)Cl-3(mu(2)-Cl). Sb2W3Cl7(mu(2)-O)(mu(3)-O)(2)(NBut)(3)(NHBut)(mu(2)-NBut)(2) (5) have been characterised. (C) 2010 Elsevier Ltd. All rights reserved.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBut)2(NHBut)2 (1) have been determined. In the gas phase, 1 adopts both C1 and C2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C2 conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives W(NBut)4[Rh(COD)]2 (3) and W(NBut)4[Pd(eta3-C3H5)]2 (4) via the dilithiated intermediate Li2[W(NBut)4] (2). In both cases, the [W(NBut)4] moiety bridges the two organometallic fragments. Reaction of 1 with Me2Zn has produced [Me(tBuN)W(mu-NBut)2ZnMe(NH2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 degrees C has formed the hitherto uncharacterized bimetallic alloy WPd2.