Exchange coupling states of cobalt complexes to control proton-coupled electron transfer.

The electrochemical proton reactivity of transition metal complexes receives significant attentions. A thorough understanding of proton-coupled electron transfer (PCET) pathways is essential for elucidating the mechanism behind a proton reduction reaction, and controlling the pathway is a key focus in the field of the catalyst development. Spin interactions within complexes, which arise during electron transfer, can affect significantly the PCET pathway. Herein, we explore the phenomenon of spin rearrangement during the electrochemical reorganization of high-spin cobalt complexes. Our findings reveal that opposing spin interactions, induced by different coordination environments, can alter the PCET pathway. Finally, detailed analysis of the PCET pathway allows us to propose mechanisms for proton reduction in high-spin cobalt complexes.