Reconciling Imbalanced and Nonadiabatic Reactivity in Transition Metal–Oxo-Mediated Concerted Proton Electron Transfer (CPET)

Abstract

Recently, there have been several experimental demonstrations of how the rates of concerted proton electron transfer (CPET) are affected by stepwise thermodynamic parameters of only proton (ΔG°_PT) or electron (ΔG°_ET) transfer. Semiclassical structure–activity relationships have been invoked to rationalize these linear free energy relationships, but it is not clear how they would manifest in a nonadiabatic reaction. Using density functional theory calculations, we demonstrate how a decrease in ΔG°_PT can lead to transition state imbalance in a nonadiabatic framework. We then use these calculations to anchor a theoretical model that reproduces experimental trends with ΔG°_PT and ΔG°_ET. Our results reconcile predictions from semiclassical transition state theory with models that treat proton transfer quantum mechanically in CPET reactivity, make new predictions about the importance of basicity for uphill CPET reactions, and suggest similar treatments may be possible for other nonadiabatic reactions.