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Hydrazine Formation via Coupling of a Nickel(III)–NH₂ Radical

Gu, Nina X. and Oyala, Paul H. and Peters, Jonas C. (2021) Hydrazine Formation via Coupling of a Nickel(III)–NH₂ Radical. Angewandte Chemie International Edition, 60 (8). pp. 4009-4013. ISSN 1433-7851. https://resolver.caltech.edu/CaltechAUTHORS:20200825-115712108

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Abstract

M(NH_x) intermediates involved in N−N bond formation are central to ammonia oxidation (AO) catalysis, an enabling technology to ultimately exploit ammonia (NH₃) as an alternative fuel source. While homocoupling of a terminal amide species (M‐NH₂) to form hydrazine (N₂H₄) has been proposed, well‐defined examples are without precedent. Herein, we discuss the generation and electronic structure of a NiIII‐NH₂ species that undergoes bimolecular coupling to generate a Ni^(II)₂(N₂H₄) complex. This hydrazine adduct can be further oxidized to a structurally unusual Ni₂(N₂H₂) species; this releases N₂ in the presence of NH₃, thus establishing a synthetic cycle for Ni‐mediated AO. Distribution of the redox load for H₂N‐NH₂ formation via NH₂ coupling between two metal centers presents an attractive strategy for AO catalysis using Earth‐abundant, late first‐row metals.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1002/anie.202013119DOIArticle
https://chemrxiv.org/articles/preprint/Hydrazine_Formation_via_NiIII-NH2_Radical_Coupling_in_Ni-Mediated_Ammonia_Oxidation/12858197OrganizationDiscussion Paper
ORCID:
AuthorORCID
Gu, Nina X.0000-0002-4637-8418
Oyala, Paul H.0000-0002-8761-4667
Peters, Jonas C.0000-0002-6610-4414
Alternate Title:Hydrazine Formation via Ni^(III)-NH₂ Radical Coupling in Ni-Mediated Ammonia Oxidation, Hydrazine Formation via Coupling of a Ni^(III)-NH₂ Radical, Hydrazine Formation via Coupling of a Nickel(III)–NH2 Radical
Additional Information:© 2020 Wiley‐VCH GmbH. Issue Online: 12 February 2021; Version of Record online: 23 December 2020; Accepted manuscript online: 05 November 2020; Manuscript received: 04 October 2020. The authors acknowledge Dr. Michael Takase and Lawrence Henling for assistance with X‐ray crystallography. This work was supported by the National Institutes of Health (General Medical Sciences, grant GM070757) and an NSF‐GRFP to N.X.G. The Caltech EPR facility is supported by the Dow Next Generation Educator Fund. The X‐Ray Crystallography Facility in the Beckman Institute at Caltech has been supported by a Dow Next Generation Instrumentation Grant. The authors declare no conflict of interest.
Funders:
Funding AgencyGrant Number
NIHGM070757
NSF Graduate Research FellowshipUNSPECIFIED
Dow Next Generation Educator FundUNSPECIFIED
Subject Keywords:ammonia oxidation; nickel; N–N bond; formation radicals
Issue or Number:8
Record Number:CaltechAUTHORS:20200825-115712108
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200825-115712108
Official Citation:Hydrazine Formation via Coupling of a Nickel(III)–NH₂ Radical. N. X. Gu, P. H. Oyala, J. C. Peters, Angew. Chem. Int. Ed. 2021, 60, 4009. DOI: 10.1002/anie.202013119
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:105101
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:25 Aug 2020 19:06
Last Modified:16 Feb 2021 23:24

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