Oxidation and reduction of some tungsten, molybdenum, and vanadium chlorides by chlorinated alkyl cyanides

Abstract

Tungsten(V) chloride is oxidised by trichloroacetonitrile to give a tungsten(VI) complex containing a tungsten-nitrogen triple bond. CCl₃·CCl₂NWCl₄,CCl₃CN; tungsten(VI) chloride gives the same complex with trichloroacetonitrile and analogous complexes with monochloroacetonitrile and 1-cyano-1,1,2-trichloroethane. The i.r. spectra of molybdenum(V) complexes formed in the reactions of trichloroacetonitrile with molybdenum(V) chloride and molybdenum(IV) chloride are interpreted on the basis of a triple molybdenum–nitrogen bond being formed. Molybdenum(V) oxytrichloride forms simple adducts with trichloroacetonitrile, but no complex could be isolated from the reaction of this ligand or 1-cyano-1,1,2-trichloroethane with vanadium(IV) chloride; this halide was reduced with mono- or di-chloroacetonitrile to give vanadium(III) adducts VCl₃,3L.