Evaluating Spin-Orbit Effects on the Thermochemistry of Proton-Coupled Electron Transfer.

ABSTRACT: Many heavy transition metal compounds are active redox catalysts. Their redox potentials can be offset by differential spin-orbit coupling (SOC) effects in the case of strong perturbation of the ground-state energy of the oxidized or the reduced state. However, SOC effects are often considered negligible in the case of organometallic species, anticipating energetically well-separated, nondegenerate spin ground states for metal ions in strong ligand fields with low symmetry. We here report a rhenium(III) aminodiphosphine complex that undergoes proton-coupled electron transfer with a phenoxyl radical as a hydrogen abstractor. Experimental derivation of the PCET thermochemistry shows a deviation from coupled-cluster computations in the range of 6 kcal·mol^-1. The deviation ca

SUBMITTER: Delony D 

PROVIDER: S-EPMC12801299 | biostudies-literature | 2026 Jan

REPOSITORIES: biostudies-literature