The investigation of reaction mechanisms involving multiple coupled electronic states is an active area of research within modern theoretical and experimental chemistry. Here, we demonstrate that nonadiabatic spin-forbidden transitions between electronic states can influence the catalytic properties of first-row transition metal clusters. To calculate relative reaction rates the combination of electronic structure methods and nonadiabatic transition state theory is used. As examples, we consider the spin-forbidden mechanism of hydrogen catalysis on the active site of [NiFe]-hydrogenase and transitions between different spin states of the active sites of rubredoxin, Ni-substituted rubredoxin and 2Fe-2S ferredoxin. The spin-forbidden transitions between the electronic states of small metal-only Fe and Ni clusters are also discussed.

Nonadiabatic spin-forbidden catalysis on bioinspired Fe and Ni clusters

247th National Meeting (2014)

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