Dialkylhydroxylamido(1—)-O,N Complexes of Tungsten(VI) with Terminal Oxo and Thio Ligands

Abstract

The compounds cis -[WO₂(R₂NO)₂] (R = Et, PhCH₂, ½C₅H₁₀) have been synthesized by the reaction of WO₂Cl₂ or [WO₂(C₅H₇O₂)₂] with the respective N,N- dialkylhydroxylamines in the presence of Et₃N. When heated with WO₂Cl₂ in refluxing MeCN , Et₂NOH undergoes dealkylation and MeCN insertion to produce cis -[WO₂(NH(Me)CN(Et)O)₂] which features the bidentate N-ethyl-N- hydroxyacetamidinato (1-)-O,N′ ligand . cis - [WS₂(R₂NO)₂] and cis -[WOS(C₅H₁₀NO)₂] can be isolated in satisfactory yields by the reaction of [WO₂(R₂NO)₂] with B₂S₃. The new compounds have been characterized by microanalysis, by infrared and elecronic spectroscopy and by ¹H, ¹³C and ¹⁸³W n.m.r.