Switching between Stepwise and Concerted Proton-Coupled Electron Transfer Pathways in Tungsten Hydride Activation

Catalytic processes to generate (or oxidize) fuels such as hydrogen are underpinned by multiple proton-coupled electron transfer (PCET) steps that are associated with the formation or activation of metal-hydride bonds. Fully understanding the detailed PCET mechanisms of metal hydride transformations holds promise for the rational design of energy-efficient catalysis. Here we investigate the detailed PCET mechanisms for the activation of the transition metal hydride complex CpW(CO)₂(PMe₃)H (Cp = cyclopentadienyl) using stopped-flow rapid mixing coupled with time-resolved optical spectroscopy. We reveal that all three limiting PCET pathways can be accessed by changing the free energy for elementary proton, electron, and proton-electron transfers through the choice of base and oxidant, with the concerted pathway occurring exclusively as a secondary parallel route. Through detailed kinetics analysis, we define free energy relationships for the kinetics of elementary reaction steps, which provide insight into the factors influencing reaction mechanism. Rate constants for proton transfer processes in the limiting stepwise pathways reveal a large reorganization energy associated with protonation/deprotonation of the metal center (λ = 1.59 eV) and suggest that sluggish proton transfer kinetics hinder access to a concerted route. Rate constants for concerted PCET indicate that the concerted routes are asynchronous. Additionally, through quantification of the relative contributions of parallel stepwise and concerted mechanisms toward net product formation, the influence of various reaction parameters on reactivity are identified. This work underscores the importance of understanding the PCET mechanism for controlling metal hydride reactivity, which could lead to superior catalyst design for fuel production and oxidation.