σ-Bonded early transition metal–carbon derivatives. Part III. Complexes of methyltungsten(VI) pentahalide, halide oxide, and halide dioxide
Abstract
Methyltungsten(VI) pentachloride has been obtained from WCl6 with HgMe2, and characterised by n.m.r. and i.r. spectroscopy. Reactions of WMeCl5 with bidentate ligands give WMeCl5·L adducts {L = Ph2P[CH2]2PPh2 or O[OP(NMe2)2]2}, while unidentate ligands give either extensive reduction [MeCN, SO(OMe)2, PO(OMe)3, or P(NMe2)3O] or chlorine–oxygen exchange reactions to WMeCl3O·L or WMeClO2·2L compounds [P(NMe2)3O, PPh3O, AsPh3O, or SMe2O]. Alkylation of WCl4O by HgMe2, ZnMe2, MgMe2, and MgMel has been investigated and shown to be dependent to a considerable extent on the solvent. The best results are obtained with MgMe2 in pentane containing 7% diethyl ether.