A Bimetallic Nickel-Gallium Complex Catalyzes CO 2 Hydrogenation via the Intermediacy of an Anionic d 10 Nickel Hydride.

Autor: Cammarota RC; Department of Chemistry, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States., Vollmer MV; Department of Chemistry, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States., Xie J; Department of Chemistry, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.; Supercomputing Institute and Chemical Theory Center, University of Minnesota , Minneapolis, Minnesota 55455, United States., Ye J; Department of Chemistry, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.; Supercomputing Institute and Chemical Theory Center, University of Minnesota , Minneapolis, Minnesota 55455, United States., Linehan JC; Pacific Northwest National Laboratory , P.O. Box 999, MS K2-57, Richland, Washington 99352, United States., Burgess SA; Pacific Northwest National Laboratory , P.O. Box 999, MS K2-57, Richland, Washington 99352, United States., Appel AM; Pacific Northwest National Laboratory , P.O. Box 999, MS K2-57, Richland, Washington 99352, United States., Gagliardi L; Department of Chemistry, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.; Supercomputing Institute and Chemical Theory Center, University of Minnesota , Minneapolis, Minnesota 55455, United States., Lu CC; Department of Chemistry, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2017 Oct 11; Vol. 139 (40), pp. 14244-14250. Date of Electronic Publication: 2017 Sep 28.
DOI: 10.1021/jacs.7b07911
Abstrakt: Large-scale CO 2 hydrogenation could offer a renewable stream of industrially important C 1 chemicals while reducing CO 2 emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel-gallium complex featuring a Ni(0)→Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO 2 to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h -1 ), compared with prior homogeneous Ni-centered catalysts. The Lewis acidic Ga(III) ion plays a pivotal role in stabilizing catalytic intermediates, including a rare anionic d 10 Ni hydride. Structural and in situ characterization of this reactive intermediate support a terminal Ni-H moiety, for which the thermodynamic hydride donor strength rivals those of precious metal hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis.
Databáze: MEDLINE
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