Hydrogenolysis of Palladium(II) Hydroxide and Methoxide Pincer Complexes

Abstract

Hydrogenolysis reactions of palladium(II) hydroxide and methoxide complexes to form water and methanol, respectively, and the corresponding palladium(II) hydride are reported. In the presence of water, 1 was found to exist in solution as a water-bridged dimer; however, kinetic studies suggest the reaction of 1 and H(2) proceeds exclusively through the hydroxide monomer to form the palladium(II) hydride and water. Computational studies suggest a four-center intramolecular proton transfer as opposed to an oxidative addition/reductive elimination pathway.