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A trans-Hyponitrite Intermediate in the Reductive Coupling and Deoxygenation of Nitric Oxide by a Tricopper–Lewis Acid Complex

Lionetti, Davide and De Ruiter, Graham and Agapie, Theodor (2016) A trans-Hyponitrite Intermediate in the Reductive Coupling and Deoxygenation of Nitric Oxide by a Tricopper–Lewis Acid Complex. Journal of the American Chemical Society, 138 (15). pp. 5008-5011. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20160418-101830823

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Abstract

The reduction of nitric oxide (NO) to nitrous oxide (N_2O) is a process relevant to biological chemistry as well as to the abatement of certain environmental pollutants. One of the proposed key intermediates in NO reduction is hyponitrite (N_2O_2^(2–)), the product of reductive coupling of two NO molecules. We report the reductive coupling of NO by an yttrium–tricopper complex generating a trans-hyponitrite moiety supported by two μ-O-bimetallic (Y,Cu) cores, a previously unreported coordination mode. Reaction of the hyponitrite species with Brønsted acids leads to the generation of N_2O, demonstrating the viability of the hyponitrite complex as an intermediate in NO reduction to N_2O. The additional reducing equivalents stored in each tricopper unit are employed in a subsequent step for N_2O reduction to N_2, for an overall (partial) conversion of NO to N_2. The combination of Lewis acid and multiple redox active metals facilitates this four electron conversion via an isolable hyponitrite intermediate.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jacs.6b01083DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.6b01083PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.6b01083PublisherSupporting Information
ORCID:
AuthorORCID
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2016 American Chemical Society. Received: January 29, 2016; Publication Date (Web): March 30, 2016. This work was supported by Caltech and the PRF (T.A.). T.A. is grateful for Sloan, Dreyfus, and Cottrell fellowships. We thank Dr. Michael K. Takase and Lawrence M. Henling for assistance with X-ray crystallography. We thank Professor Jonas C. Peters for use of two infrared spectrometers. D.L. gratefully acknowledges a graduate fellowship from the Resnick Sustainability Institute at Caltech. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF Chemistry Research Instrumentation award to Caltech (CHE-0639094). The authors declare no competing financial interest.
Group:Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
CaltechUNSPECIFIED
American Chemical Society Petroleum Research FundUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
Cottrell Scholar of Research CorporationUNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
NSFCHE-0639094
Issue or Number:15
Record Number:CaltechAUTHORS:20160418-101830823
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160418-101830823
Official Citation:A trans-Hyponitrite Intermediate in the Reductive Coupling and Deoxygenation of Nitric Oxide by a Tricopper–Lewis Acid Complex Davide Lionetti, Graham de Ruiter, and Theodor Agapie Journal of the American Chemical Society 2016 138 (15), 5008-5011 DOI: 10.1021/jacs.6b01083
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:66239
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:18 Apr 2016 18:54
Last Modified:03 Oct 2019 09:54

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