A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d(10) Nickel Hydride.

Title A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d(10) Nickel Hydride.
Authors R.C. Cammarota; M.V. Vollmer; J. Xie; J. Ye; J.C. Linehan; S.A. Burgess; A.M. Appel; L. Gagliardi; C.C. Lu
Journal J Am Chem Soc
DOI 10.1021/jacs.7b07911
Abstract

Large-scale CO2 hydrogenation could offer a renewable stream of industrially important C1 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.

Citation R.C. Cammarota; M.V. Vollmer; J. Xie; J. Ye; J.C. Linehan; S.A. Burgess; A.M. Appel; L. Gagliardi; C.C. Lu.A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d(10) Nickel Hydride.. J Am Chem Soc. 2017. doi:10.1021/jacs.7b07911

Related Elements

Gallium

31 Ga 69.723000000 Gallium

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Nickel

28 Ni 58.693400000 Nickel

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Related Forms & Applications

Hydrides
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