Anomalous Reactions of Triphenylchlorosilane with Metal Carbonyl Anions

Abstract

Silyl halides react in an anomalous fashion with most metal carbonyl anions to give disiloxanes. The metal carbonyl anion may rearrange to polynuclear anions, abstract hydrogen from the solvent or other sources, be oxidized to the dimer or higher oligomers, or be halogenated by the silyl halide. Increasing the nucleophilicity of the metal carbonyl anion by phosphine substitution was thought to be a possible mechanism for suppressing the anomalous reaction, but only tricarbonyltriphenyl-phosphinecobaltate(l —) gives a normal substitution product. Germanium and tin halides give smooth substitution reactions except when bulky substituents on the anion cause severe steric hindrance. © 1972, American Chemical Society. All rights reserved.