Experimental and computational study of a direct O2-coupled Wacker oxidation: water dependence in the absence of Cu salts

Abstract

The kinetics of the Pd[(-)-sparteine]Cl(2) catalyzed oxidation of decene using oxygen as the sole oxidant have been studied in the absence of copper salts and high [Cl(-)]. Saturation kinetics are observed for [decene] as well as a third order dependence on [water]. A mechanism is proposed involving the dissociation of two chlorides and rate-limiting formation of a three-water hydrogen bridged network and subsequent oxypalladation as supported by computational studies.