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Hydrazine Formation via Coupling of a Ni^(III)-NH₂ Radical

Gu, Nina X. and Oyala, Paul H. and Peters, Jonas C. (2020) Hydrazine Formation via Coupling of a Ni^(III)-NH₂ Radical. Angewandte Chemie International Edition . ISSN 1433-7851. (In Press) 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 Ni^(III)–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; the latter 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
Additional Information:© 2020 Wiley‐VCH GmbH. Accepted manuscript online: 05 November 2020; Manuscript accepted: 05 November 2020; Manuscript revised: 04 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.
Funders:
Funding AgencyGrant Number
NIHGM070757
NSF Graduate Research FellowshipUNSPECIFIED
Dow Next Generation Educator FundUNSPECIFIED
Subject Keywords:Ammonia oxidation; N-N Coupling; Amide Coupling; Metalloradicals; Nickel(III)
Record Number:CaltechAUTHORS:20200825-115712108
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200825-115712108
Official Citation:Gu, N., Oyala, P. and Peters, J. (2020), Hydrazine (N2H4) Formation via Coupling of a NiIII‐NH2 Radical. Angew. Chem. Int. Ed. Accepted Author Manuscript. 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:05 Nov 2020 21:09

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