Organometallic Electrochemistry. I. Derivatives of Group IV-B Elements

Abstract

Organometallic derivatives of group IV elements have been studied via polarography, controlled potential electrolysis, and triangular voltammetry. Some subvalent organometals and anions have been generated and examined. In particular, the triphenylmetal radicals, Ph3M ּ (where M = Si, Ge, Sn, Pb), have been shown to suffer quite dissimilar fates in dimethoxyethane. Abstraction (Si, Ge), coupling (Sn), and arylation of the Hg electrode (Pb) have been observed. Organometallic assemblies of the type Ph3M-Bu4N+ (where M = Ge, Sn) have been shown to serve as electron-transfer reagents in reactions with other group IV halides rather than as nucleophiles. Reduction of R2SnCl2 proceeds via (R2SnCl), which rapidly dimerizes, providing a route to R2Sn(Cl)Sn-(Cl)R2 species. Reduction of Ph2MX2 leads to Ph2MH2 (M = Si, Ge), or arylation (Pb). © 1966, American Chemical Society. All rights reserved.