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Title: A Bimetallic Nickel–Gallium Complex Catalyzes CO 2 Hydrogenation via the Intermediacy of an Anionic d 10 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-centred catalysts. The Lewis acidic Ga(III) ion plays a pivotal role by stabilizing reactive catalytic intermediates, including a rare anionic d10 Ni hydride. The structure of this reactive intermediate shows a terminal Ni-H, for which the 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. The work was supported as part of the Inorganometallic Catalysis 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. R.C.C. and M.V.V. were supported by DOE Office of Science Graduate Student Research and National Science Foundation Graduate Researchmore » Fellowship programs, respectively. 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. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3];  [3]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
  2. 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
  3. Pacific Northwest National Laboratory, P.O. Box 999, MS K2-57, Richland, Washington 99352, United States
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1414521
Report Number(s):
PNNL-SA-127919
Journal ID: ISSN 0002-7863; KC0302010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 139; Journal Issue: 40
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cammarota, Ryan C., Vollmer, Matthew V., Xie, Jing, Ye, Jingyun, Linehan, John C., Burgess, Samantha A., Appel, Aaron M., Gagliardi, Laura, and Lu, Connie C.. A Bimetallic Nickel–Gallium Complex Catalyzes CO 2 Hydrogenation via the Intermediacy of an Anionic d 10 Nickel Hydride. United States: N. p., 2017. Web. doi:10.1021/jacs.7b07911.
Cammarota, Ryan C., Vollmer, Matthew V., Xie, Jing, Ye, Jingyun, Linehan, John C., Burgess, Samantha A., Appel, Aaron M., Gagliardi, Laura, & Lu, Connie C.. A Bimetallic Nickel–Gallium Complex Catalyzes CO 2 Hydrogenation via the Intermediacy of an Anionic d 10 Nickel Hydride. United States. doi:10.1021/jacs.7b07911.
Cammarota, Ryan C., Vollmer, Matthew V., Xie, Jing, Ye, Jingyun, Linehan, John C., Burgess, Samantha A., Appel, Aaron M., Gagliardi, Laura, and Lu, Connie C.. Thu . "A Bimetallic Nickel–Gallium Complex Catalyzes CO 2 Hydrogenation via the Intermediacy of an Anionic d 10 Nickel Hydride". United States. doi:10.1021/jacs.7b07911.
@article{osti_1414521,
title = {A Bimetallic Nickel–Gallium Complex Catalyzes CO 2 Hydrogenation via the Intermediacy of an Anionic d 10 Nickel Hydride},
author = {Cammarota, Ryan C. and Vollmer, Matthew V. and Xie, Jing and Ye, Jingyun and Linehan, John C. and Burgess, Samantha A. and Appel, Aaron M. and Gagliardi, Laura and Lu, Connie C.},
abstractNote = {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-centred catalysts. The Lewis acidic Ga(III) ion plays a pivotal role by stabilizing reactive catalytic intermediates, including a rare anionic d10 Ni hydride. The structure of this reactive intermediate shows a terminal Ni-H, for which the 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. The work was supported as part of the Inorganometallic Catalysis 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. R.C.C. and M.V.V. were supported by DOE Office of Science Graduate Student Research and National Science Foundation Graduate Research Fellowship programs, respectively. 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. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.},
doi = {10.1021/jacs.7b07911},
journal = {Journal of the American Chemical Society},
number = 40,
volume = 139,
place = {United States},
year = {Thu Sep 28 00:00:00 EDT 2017},
month = {Thu Sep 28 00:00:00 EDT 2017}
}