Supporting Information for Ligand effects on Decarbonylation of Palladium-acyl Complexes

Abstract

These files contain primary data along with associated output from instrumentation supporting all results reported in "Ligand effects on Decarbonylation of Palladium-acyl Complexes". In this work we found: The influences of perturbations of supporting phosphine ligands on the dehydrative decarbonylation of (Ln)Pd(II)(Cl)-hydrocinnamoyl com-plexes (L = PtBu3, n = 1; L = PPh3, n = 2; L = dppe, n = 1) to yield styrene were studied through combined experiment and theory. Abstraction of chloride from the complexes by silver and zinc salts, as well as sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, enhanced the efficiency of styrene formation, according to the trend in L: PtBu3 > dppe > PPh3. DFT calculations corroborated the experimental findings and provided insights into the ligand influences on reaction step barriers and transition state structures. Key findings include: a stable intermediate forms after chloride abstraction, from which -hydride elimination is rate-determining, the low coordination number for the PtBu3 case lowers reaction barriers for all steps, and the trans disposition of two ligands for L = PPh3 contributes to low efficiency for styrene production in that case.