Developing catalysts that utilize earth-abundant first-row transition metals is becoming an increasingly important area of study. Early/late heterobimetallic complexes provide a potential avenue to overcome the propensity of base metals to undergo one-electron processes. The Lewis acid/base interactions between the two disparate metals in such complexes facilitate the two-electron redox processes necessary for bond cleavage and formation while two metal binding sites are available for substrate binding. With this motivation, a series of Ti/M (M = Fe, Ni, Cu) heterobimetallic complexes have been synthesized using a bis(phosphinoamide) ligand scaffold. The bis(phosphinoamide) framework allows for an extra open coordination site on the late metal while supporting metal-metal bonding. Metal-metal cooperative reactivity will be discussed in the context of the newly synthesized bimetallic compounds and small molecule activation and catalysis.

Synthesis, characterization, and reactivity of Ti/M heterobimetallic complexes

ACS Fall 2021

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