Carboxylic Solvents and O-Donor Ligand Effects on CH Activation by Pt(II)

Abstract
We report on the design of more efficient C-H activation catalysts based on DFT calculations. The first examples of well-defined, N,O-donor ligated platinum complexes that are competent for fast C-H activation are detailed. These complexes exhibit thermal and protic stability and are efficient catalysts for H/D exchange reactions with benzene. The C-H activation is shown to benefit from design elements that (A) reduce the barrier for substrate coordination and (B) retain a low barrier for CH cleavage via a novel six-membered transition state involving the carboxylate group of the solvent.