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  • Spectroscopic Evidence of Hyponitrite Radical Intermediate in NO Disproportionation at a MOF‐Supported Mononuclear Copper Site
Title: Spectroscopic Evidence of Hyponitrite Radical Intermediate in NO Disproportionation at a MOF‐Supported Mononuclear Copper Site
Abstract Dianionic hyponitrite (N2O22−) is often proposed, based on model complexes, as the key intermediate in reductive coupling of nitric oxide to nitrous oxide at the bimetallic active sites of heme‐copper oxidases and nitric oxide reductases. In this work, we examine the gas‐solid reaction of nitric oxide with the metal–organic framework CuI‐ZrTpmC* with a suite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N2O2.−intermediate. These results highlight the advantage provided by site‐isolation in metal–organic frameworks (MOFs) for studying important reaction intermediates, and provide a mechanistic scenario compatible with the proposed one‐electron couple in these enzymes.  more » « less
Award ID(s):
1645232
PAR ID:
10236455
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie International Edition
Volume:
60
Issue:
14
ISSN:
1433-7851
Page Range / eLocation ID:
p. 7845-7850
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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