Reactions of aluminopolyhydride complexes of tungsten. X-Ray crystal structures of [(Me3P)3H3W(µ-H)2AlCl(µ-NCHEt)]2, {[(Me3P)3WH5]Li}4, WH2I(PMe3)3(SiMe3), and (Me3P)3H2W(µ-H)3AlCl2(NMe3)

Abstract

The aluminopolyhydride complex [(Me₃P)₃H₃W(µ-H)₂AlH (µ-H)]₂ reacts with RCN (R = Me or Et) to give the µ-amido complexes [(Me₃P)₃H₃W(µ-H)₂AlH (µ-NCHR)]₂; the structure of [(Me₃P)₃H₃W(µ-H)₂AlCl(µ-NCHEt)]₂ obtained from chloride-containing solutions has been determined. Reaction of the aluminopolyhydride with lithium alkyls gives {[(Me₃P)₃WH₅]Li}₄, and this compound reacts with Me₃SiCH₂I to give WH₂I(PMe₃)₃(SiMe₃); the structures of both products have been determined. Interaction of the polyhydride with NMe₃HCl gives (Me₃P)₃H₂W(µ-H)₃AlCl₂(NMe₃) which also has been structurally characterised. Cyclohexanone gives the monomer (Me₃P)₄W(µ-H)₂AlH₃. Proton, ³¹P, and ²⁷Al n.m.r. and i.r. spectra of the compounds have been recorded.