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Direct Resonance Raman Characterization of a Peroxynitrito Copper Complex Generated from O 2 and NO and Mechanistic Insights into Metal‐Mediated Peroxynitrite Decomposition
Author(s) -
Liu Jeffrey J.,
Siegler Maxime A.,
Karlin Kenneth D.,
MoënneLoccoz Pierre
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201904672
Subject(s) - homolysis , chemistry , raman spectroscopy , moiety , copper , metal , peroxynitrite , stereochemistry , resonance (particle physics) , radical , photochemistry , organic chemistry , superoxide , physics , particle physics , optics , enzyme
We report the formation of a new copper peroxynitrite ( PN ) complex [Cu II (TMG 3 tren)(κ 1 ‐OONO)] + ( PN1 ) from the reaction of [Cu II (TMG 3 tren)(O 2 .− )] + ( 1 ) with NO . (g) at −125 °C. The first resonance Raman spectroscopic characterization of such a metal‐bound PN moiety supports a cis κ 1 ‐( − OONO) geometry. PN1 transforms thermally into an isomeric form ( PN2 ) with κ 2 ‐O,O′‐( − OONO) coordination, which undergoes O−O bond homolysis to generate a putative cupryl (LCu II −O . ) intermediate and NO 2 . . These transient species do not recombine to give a nitrato (NO 3 − ) product but instead proceed to effect oxidative chemistry and formation of a Cu II –nitrito (NO 2 − ) complex ( 2 ).