Metal-Alkyl and Metal-Hydride Bond Formation and Fission;Oxidative Addition and Reductive Elimination

Abstract

A premiere area of organotransition metal chemistry is the scission and formation of C—C, C—H, and H—H bonds of organic substrates. These transformations have been demonstrated to be accessible through the use of coordinatively unsaturated organometallic fragments as shown in Eq. (1), where R, R’ = alkyl, aryl, H, etc. Mechanistic aspects of this reaction have still not been fully appreciated

$${{L}_{n}}M + R - R\prime \rightleftharpoons [{{L}_{n}}M(R)(R\prime )]$$

(1)

However, the discovery of o-coordination by H2 is an important recent advance in this area. The three-center, two-electron “bond” is also recognized in intramolecular agostic C—H metal interactions. Recently evidence has been mounting in support of a C—H o-interaction for “free” hydrocarbons (vide infra).