Comparison of the reactivities of neutral and cationic transition metal alkyls and hydrides

Abstract

Comparisons of the reactivities of neutral and cationic alkyl- and aryl-palladium and platinum complexes revealed that the creation of a vacant site adjacent to the alkyl or aryl ligand bound to the palladium center causes marked enhancement in the reactivities of these Group 10 metal alkyls and aryls toward β-hydrogen elimination, and olefin or CO insertion. The implications of the results on the fundamental processes of the transition metal alkyls and aryls with the mechanisms of palladium-catalyzed organic synthesis such as arylation of olefins and carbonylation of aryl halides are discussed. Comparisons of the reactivities of the neutral and cationic ruthenium hydrides also indicated enhancement in reactivity of the neutral hydride complex by its conversion to a cationic complex.