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H₂ Evolution from a Thiolate-Bound Ni(III) Hydride

Gu, Nina X. and Oyala, Paul H. and Peters, Jonas C. (2020) H₂ Evolution from a Thiolate-Bound Ni(III) Hydride. Journal of the American Chemical Society, 142 (17). pp. 7827-7835. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20200406-103934930

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Abstract

Terminal Ni^(III) hydrides are proposed intermediates in proton reduction catalyzed by both molecular electrocatalysts and metalloenzymes, but well-defined examples of paramagnetic nickel hydride complexes are largely limited to bridging hydrides. Herein, we report the synthesis of an S = 1/2, terminally bound thiolate–Ni^(III)–H complex. This species and its terminal hydride ligand in particular have been thoroughly characterized by vibrational and EPR techniques, including pulse EPR studies. Corresponding DFT calculations suggest appreciable spin leakage onto the thiolate ligand. The hyperfine coupling to the terminal hydride ligand of the thiolate–Ni^(III)–H species is comparable to that of the hydride ligand proposed for the Ni–C hydrogenase intermediate (Ni^(III)–H–Fe^(II)). Upon warming, the featured thiolate–Ni^(III)–H species undergoes bimolecular reductive elimination of H₂. Associated kinetic studies are discussed and compared with a structurally related Fe^(III)–H species that has also recently been reported to undergo bimolecular H–H coupling.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.0c00712DOIArticle
ORCID:
AuthorORCID
Gu, Nina X.0000-0002-4637-8418
Oyala, Paul H.0000-0002-8761-4667
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2020 American Chemical Society. Received: January 19, 2020; Published: April 4, 2020. The authors acknowledge Gerri Roberts for preliminary data and Dr. Michael Takase and Lawrence Henling for assistance with X-ray crystallography. This work was supported by the Department of Energy (DOE-0235032) and NSF-GRFP (N.X.G.). The Caltech EPR facility was supported by the NSF (NSF-1531940) and the Dow Next Generation Educator Fund. The X-ray Crystallography Facility in the Beckman Institute at Caltech was supported by the Dow Next Generation Instrumentation Grant. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DOE-0235032
NSF Graduate Research FellowshipUNSPECIFIED
NSF153194
Dow Next Generation Educator FundUNSPECIFIED
Issue or Number:17
Record Number:CaltechAUTHORS:20200406-103934930
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200406-103934930
Official Citation:H2 Evolution from a Thiolate-Bound Ni(III) Hydride. Nina X. Gu, Paul H. Oyala, and Jonas C. Peters. Journal of the American Chemical Society 2020 142 (17), 7827-7835; DOI: 10.1021/jacs.0c00712
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:102349
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:06 Apr 2020 18:09
Last Modified:29 Apr 2020 17:05

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