The Mechanism of the Decomposition of Organometallic Compounds of Transition Metals and the Role of Intermediate Species in Catalysis

The three pathways leading to the decomposition of organometallic compounds of transition metals (Mo, W, Ta, Re, Pt, Pd, Rh, Cr, Nd, Y, and Nb) at the instant of formation are examined. α-Decomposition accompanied by the formation of carbene and carbyne species is of decisive importance for methyl, benzyl, trimethylsilylmethyl, and neophyl derivatives. The decomposition proceeds without superposition of radical stages. The mechanism of the chain metathesis of olefins and cycloolefins under the influence of carbene complexes of transition metals is considered. Ideas concerning the chemical nature of the elementary steps in the hydrogenolysis and isomerisation of the carbon skeleton and the dehydrogenation and hydrogenation of hydrocarbons are put forward on the basis of the hypothesis that the primary step in the oxidative addition of hydrocarbons to zerovalent metals involves the formation of organometallic compounds.
The bibliography includes 108 references.