Binuclear transition metal complexes containing Metal–Metal bonds: Understanding the fundamental aspects and Metal–Metal cooperativity in catalysis

Abstract

Binuclear transition metal complexes featuring metal–metal bonds exhibit distinct structural and electronic properties that significantly influence their reactivity and catalytic performance. This review explores the fundamental aspects of these complexes, with a focus on the nature of metal–metal interactions, which can vary from weak to strong based on the metal identities, oxidation states, and ligand environments. Furthermore, the review delves into basic redox processes, bond activation, and catalytic applications, considering the cooperative effect of the second metal center. The review also includes case studies of important catalytic processes, such as hydrogenation, hydroformylation, nucleophilic addition and substitution, cross coupling reactions, polymerization, carbene and nitrene transfer reactions, and CH bond activation and functionalization, to illustrate the role of metal–metal cooperativity in facilitating these transformations. These insights provide a comprehensive understanding of the design of next-generation catalysts with enhanced efficiency and selectivity.