Mechanism of Olefin Hydrogenation Catalyzed by RuHCl(L)(PR3)2 Complexes (L = CO, PR3): A DFT Study

Abstract

A DFT study of the full catalytic cycle for H2–hydrogenation of ethylene by RuHCl(CO)(PR3)2 (3a) and RuHCl(PH3)(PR3)2 (4a) (R = iPr) catalysts indicates that H2 binding precedes and stabilizes ethylene insertion, and ethane loss proceeds through a readily accessible Ru(IV) dihydride intermediate. A comparison of the CO and PH3 reaction coordinates also reveals that the latter is systematically more stable.