Small molecule activation with bimetallic systems: a landscape of cooperative reactivity

Abstract

There is growing interest in the design of bimetallic cooperative complexes, which have emerged due to their potential for bond activation and catalysis, a feature widely exploited by nature in metalloenzymes, and also in the field of heterogeneous catalysis. Herein, we discuss the widespread opportunities derived from combining two metals in close proximity, ranging from systems containing multiple M-M bonds to others in which bimetallic cooperation occurs even in the absence of M⋯M interactions. The choice of metal pairs is crucial for the reactivity of the resulting complexes. In this context, we describe the prospects of combining not only transition metals but also those of the main group series, which offer additional avenues for cooperative pathways and reaction discovery. Emphasis is given to mechanisms by which bond activation occurs across bimetallic structures, which is ascribed to the precise synergy between the two metal atoms. The results discussed herein indicate a future landscape full of possibilities within our reach, where we anticipate that bimetallic synergism will have an important impact in the design of more efficient catalytic processes and the discovery of new catalytic transformations. © 2022 The Royal Society of Chemistry.