Direct Resonance Raman Characterization of a Peroxynitrito Copper Complex Generated from O 2  and NO and Mechanistic Insights into Metal‐Mediated Peroxynitrite Decomposition | Zendy

Liu Jeffrey J. | Zendy; Siegler Maxime A. | Zendy; Karlin Kenneth D. | Zendy; MoënneLoccoz Pierre | Zendy

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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 ).

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