Physical organic chemistry of transition metal carbene complexes. 2. Kinetics and mechanism of reactions of [methoxy(phenyl)carbene]pentacarbonylchromium(0) with primary aliphatic amines in aqueous acetonitrile

Abstract

A kinetic study of the aminolysis of [methoxy(phenyl)carbene]pentacarbonylchromium(O) with five primary aliphatic amines in 20% acetonitril-80% water (v/v) at 25 o C is reported. Second-order rate constants (k A ) increase with amine and OH - concentration, which indicates general base catalysin. Plots of k A vs amine or OH - concentration are curved and level off at high concentration; this implies a change in rate-limiting step and demonstrates that the reaction is stepwise