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Spectroscopic Evidence of Hyponitrite Radical Intermediate in NO Disproportionation at a MOF‐Supported Mononuclear Copper Site
Author(s) -
Sun Chenyue,
Yang Luming,
Ortuño Manuel A.,
Wright Ashley M.,
Chen Tianyang,
Head Ashley R.,
López Núria,
Dincă Mircea
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202015359
Subject(s) - chemistry , disproportionation , bimetallic strip , copper , nitric oxide , metal organic framework , inorganic chemistry , metal , oxide , photochemistry , catalysis , organic chemistry , adsorption
Abstract Dianionic hyponitrite (N 2 O 2 2− ) 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 Cu I ‐ZrTpmC* with a suite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N 2 O 2 .− 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.