The Effect of the cis-donor in pincer ligands on hydrogenolysis of Pd-OH: A DFT study

A series of pincer-Pd-OH complexes containing strongly-bound cis-donor ligands is shown by DFT to undergo hydrogenolysis via an internal electrophilic substitution pathway. Use of hemilabile cis-ligands does not lead to hydrogenolysis of the Pd-OH bond, but rather hydrogenation to produce a water-bound Pd-H, matching the experimental results.87