The chemistry of rhenium–nitrile complexes

Abstract

Rhenium pentachloride is reduced by nitriles to tetrachlorobis(alkanonitrile)rhenium(IV). The oxidation product is an organic chloro-compound. Several new rhenium(IV) complexes were obtained by substitution or by addition of nucleophiles to the co-ordinated nitrile group. Addition of primary aromatic amines gives complexes of N-substituted amidines and of alcohols, complexes of imidate esters. Reduction of the complex ReCl₄(MeCN)₂ gives the tetrachlorobis(acetonitrile)rhenate(III) ion, which has been isolated in crystalline salts. Malononitrile reacts with trans-ReOCl₃(PPh₃)₂ to give trichloro-[4-(dicyanomethylene)azetid-2-imine]bis(triphenylphosphine)-rhenium(III); this complex with ammonia gives a novel ammine salt.