A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride

Ryan C. Cammarota; Matthew V. Vollmer; Jing Xie; Jingyun Ye; John C. Linehan; Samantha A. Burgess; Aaron M. Appel; Laura Gagliardi; Connie C. Lu

doi:10.1021/jacs.7b07911

A Bimetallic Nickel-Gallium Complex Catalyzes CO₂ Hydrogenation via the Intermediacy of an Anionic d¹⁰ Nickel Hydride

Ryan C. Cammarota, Matthew V. Vollmer, Jing Xie, Jingyun Ye, John C. Linehan, Samantha A. Burgess, Aaron M. Appel, Laura Gagliardi, Connie C. Lu

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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 d¹⁰ 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.

Original language	English (US)
Pages (from-to)	14244-14250
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	139
Issue number	40
DOIs	https://doi.org/10.1021/jacs.7b07911
State	Published - Oct 11 2017

Bibliographical note

Funding Information:
R.C.C. and M.V.V. were supported by DOE Office of Science Graduate Student Research and National Science Foundation (NSF) Graduate Research Fellowship programs, respectively. J.X., J.Y., and L.G. were supported as part of 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 under Award DE-SC0012702. J.C.L., S.A.B., and A.M.A. were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. C.C.L. acknowledges the NSF (CHE-1665010) for support. The authors acknowledge Dr. Victor Young, Jr. for assistance with X-ray crystallography. R.C.C. thanks Dr. Christopher Zall and Dr. Eric Wiedner for helpful suggestions. C.C.L. thanks Dr. Morris Bullock (PNNL) for cosponsoring the DOE graduate research fellowship to R.C.C.

Publisher Copyright:
© 2017 American Chemical Society.

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title = "A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride",

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 d10 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.",

author = "Cammarota, {Ryan C.} and Vollmer, {Matthew V.} and Jing Xie and Jingyun Ye and Linehan, {John C.} and Burgess, {Samantha A.} and Appel, {Aaron M.} and Laura Gagliardi and Lu, {Connie C.}",

note = "Funding Information: R.C.C. and M.V.V. were supported by DOE Office of Science Graduate Student Research and National Science Foundation (NSF) Graduate Research Fellowship programs, respectively. J.X., J.Y., and L.G. were supported as part of 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 under Award DE-SC0012702. J.C.L., S.A.B., and A.M.A. were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. C.C.L. acknowledges the NSF (CHE-1665010) for support. The authors acknowledge Dr. Victor Young, Jr. for assistance with X-ray crystallography. R.C.C. thanks Dr. Christopher Zall and Dr. Eric Wiedner for helpful suggestions. C.C.L. thanks Dr. Morris Bullock (PNNL) for cosponsoring the DOE graduate research fellowship to R.C.C. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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AU - Appel, Aaron M.

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N2 - 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 d10 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.

AB - 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 d10 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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A Bimetallic Nickel-Gallium Complex Catalyzes CO₂ Hydrogenation via the Intermediacy of an Anionic d¹⁰ Nickel Hydride

Abstract

Bibliographical note

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Energy Frontier Research Center For Inorganometallic Catalyst Design (DE-SC0012702)

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A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride

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Bibliographical note

UN SDGs

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Energy Frontier Research Center For Inorganometallic Catalyst Design (DE-SC0012702)

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A Bimetallic Nickel-Gallium Complex Catalyzes CO₂ Hydrogenation via the Intermediacy of an Anionic d¹⁰ Nickel Hydride