期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 139, 期 40, 页码 14244-14250出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b07911
关键词
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资金
- DOE Office of Science
- National Science Foundation (NSF)
- Inorganometallic Catalyst Design Center, an Energy Frontier Research Center - U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences [DE-SC0012702]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences Biosciences
- NSF [CHE-1665010]
- DOE
Large-scale CO2 hydrogenation could offer a renewable stream of industrially important C-1 chemicals while reducing CO2 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 CO2 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.
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