A new route to prepare the mixed oxo-ethylidyne-capped trinuclear tungsten(IV) cluster and the crystal structure of H2Na3[W3O(CCH3)-(O2CCH3)6(H2O)3][H2W12O40]·13.5H2O†
This work was done in Fuzhou Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences.
Abstract
The synthesis and the structural characterization of the title compound H2Na3[W3O(CCH3)-(O2CCH3)6(H2O)3][H2W12O40]·13.5H2O are described. It is known that the mixed oxo-ethylidynecapped tritungsten cluster can be obtained by Zn dust reduction of Na2WO4·2H2O in acetic anhydride. The title compound has been characterized by X-ray diffraction, UV/VIS and 1H NMR spectra. The tungsten atoms in the cluster cation and anion are in the oxidation states of W(IV) and W(VI) respectively. The crystal is rhombohedral with the space group R32, a = 17.058 (3)Å, c = 49.665 (9)Å, γ=120°, V=12516(9)Å3, Z=6, final R = 0.037 for 2071 reflections with I ≥3σ (I). Both the cluster cation and anion have a C3 symmetry. The important interatomic distances in angstroms for the cluster cation are: W—W, 2.730(2); W—μ3−O, 2.00; W—O (carboxy1), 2.12; W—Ot 2.18 (2).
