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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 N2 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.
Bibliographical noteFunding Information:
The authors thank Prof. Laura Gagliardi, Dr. Varinia Bernales, and Dr. Konstantinos D. Vogiatzis for computational insight. The work covered in this review was supported in part by the National Science Foundation (NSF, CHE-1254621) and by the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award DE-SC0012702. L.J.C. was supported by a Doctoral Dissertation Fellowship (University of Minnesota Graduate School).
- Lewis acid
- Metal-metal bonding