Time resolved spectroscopic studies relevant to reactive intermediates in homogeneous catalysis. The migratory insertion reaction

摘要

A major challenge of mechanistic organometallic chemistry is to characterize the structure and dynamics of reactive intermediates in stoichiometric and catalytic processes. In this context, time resolved spectroscopic techniques can be used to investigate reactive intermediates generated by laser flash photolysis of suitable organometallic precursors. Specific examples will be drawn from ongoing mechanistic research in these laboratories in which time-resolved infrared (TRIR) and time-resolved optical (TRO) detection are used to probe the reactivities and structures of intermediates in the carbonylations of metal-alkyl bonds, a key pathway in catalytic activation of carbon monoxide. The principal focus will be upon the migratory insertion mechanisms of cobalt carbonyl complexes similar to those used in alkene hydroformylation catalysis as well as model systems based on manganese carbonyls.