Kinetics of initiation of the third generation Grubbs metathesis catalyst: convergent associative and dissociative pathways

The kinetics of the nominally irreversible reaction of the third generation Grubbs catalyst G-III-Br (4.6 mu M) with ethyl vinyl ether (EVE) in toluene at 5 degrees C have been re-visited. There is a rapid equilibrium between the bispyridyl form of G-III-Br, 1, and its monopyridyl form, 2 (K approximate to 0.001 M). The empirical rate constants (k(obs.)) for the reaction with EVE, determined UV-vis spectrophotometrically under optimised anaerobic stopped-flow conditions, are found by testing the quality of fit of a series of steady-state approximations. The kinetics do not correlate with solely dissociative or associative pathways, but do correlate with a mechanism where these pathways converge at an alkene complex primed to undergo metathesis. In the presence of traces of air there is a marked increased in the rate of decay of G-III-Br due to competing oxidation to yield benzaldehyde; a process that appears to be very efficiently catalysed by trace metal contaminants. The apparent acceleration of the initiation process may account for the rates determined herein being over an order of magnitude lower than previously estimated.