The formation and cleavage of chemical bonds in catalytic reactions relies on accessible redox processes that are often challenging for base metals such as first row and early transition metals. Bimetallic cooperativity provides a potential solution to this challenge. Leveraging dinucleating phosphinoamide ligands, a series of early/late heterobimetallic Zr/Co compounds have been synthesized and investigated. These frameworks have been shown to support metal-metal multiple bonds and facilitate redox and small molecule application processes.

Proton-coupled electron transfer (PCET) is a central principle for catalytic hydrogen and CO2 transformations. In this seminar, I will discuss how internal factors of metal–ligand identity, coordination geometry, and spin states interact with external influences such as pKa of proton donors and applied potentials to shape PCET pathways. Our studies with Co complexes show that spin interactions critically govern electron transfer, while investigations of Fe complexes reveal how maintaining the low spin states enables rapid, efficient multi-electron processes.