Elucidating Proton-Coupled Electron Transfer Mechanisms of Metal Hydrides with Free-energy and Pressure Dependent Kinetics

Proton-coupled electron transfer (PCET) was studied in a series of tungsten hydride complexes with pendant pyridyl arms ([(PyCH2Cp)WH(CO)3], PyCH2Cp = pyridylmethylcyclopentadienyl), triggered by laser flash-generated RuIII-tris-bipyridine oxidants, in acetonitrile solution. The free energy dependence of the rate constant and the kinetic isotope effects (KIEs) showed that the PCET mechanism could be switched between concerted and the two stepwise PCET mechanisms (electron-first or proton-first) in a predictable fashion. Straightforward and general guidelines for how the relative rates of the different mechanisms depend on oxidant and base are presented. The rate of the concerted reaction should depend symmetrically on changes in oxidant and base strength, that is on the overall ΔG0PCET, and we argue that an “asynchronous” behavior would not be consistent with a model where the electron and proton tunnel from a common transition state. The observed rate constants and KIEs were examined as a function of hyd...