Metal hydride complexes are key intermediates in transition-metal catalyzed reactions that activate small molecules, such as proton reduction and CO<sub>2</sub> reduction. Formation—and reactivity—of metal hydride complexes involves proton-coupled electron transfer processes that can proceed via stepwise or concerted routes. To optimize efficiency in the catalytic reactions that mediate fuel production, this proton-electron reactivity must be carefully orchestrated. We have applied electrochemical methods and time-resolved spectroscopy to identify the dominant proton-coupled electron transfer reaction pathways for a tungsten hydride complex. We reveal that by changing the strength of the base and the oxidant, different reaction pathways can be accessed, with the reaction kinetics of elementary proton and electron transfer steps influenced by the thermochemical parameters. This work reveals how reaction mechanism and kinetics can be modulated across a two-dimensional parameter space.

Switching the mechanism: Proton-coupled electron transfer reactivity of a tungsten hydride complex

255th National Meeting (2018)

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