Leveraging molecular metal–support interactions for H 2 and N 2 activation

Abstract Many challenging chemical reactions require precious metal catalysts to proceed. Bio-inspired catalysts featuring multiple earth-abundant metals are an attractive alternative, as they offer boundless possibilities for facilitating processes that the constituent metals cannot mediate on their own. Our work utilizes a supporting metal as an electronic lever for tuning a base metal (Co, Ni) active site via a metal–metal bond. This approach has allowed for the development of metal–support catalysts for reductive N 2 silylation and olefin hydrogenation. The bimetallic catalysts display markedly enhanced activity compared to the analogous single metal centers. In this review, we investigate the role of the supporting metal in substrate binding, activation, and catalysis to inform future efforts in the development and optimization of molecular metal–support catalysts.