Direct Resonance Raman Characterization of a Peroxynitrito Copper Complex Generated from O <subscript>2</subscript> and NO and Mechanistic Insights into Metal-Mediated Peroxynitrite Decomposition.
In: Angewandte Chemie (International ed. in English), Jg. 58 (2019-08-05), Heft 32, S. 10936-10940
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Zugriff:
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).
(© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
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Direct Resonance Raman Characterization of a Peroxynitrito Copper Complex Generated from O <subscript>2</subscript> and NO and Mechanistic Insights into Metal-Mediated Peroxynitrite Decomposition.
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Autor/in / Beteiligte Person: | Liu, JJ ; Siegler, MA ; Karlin, KD ; Moënne-Loccoz, P |
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Zeitschrift: | Angewandte Chemie (International ed. in English), Jg. 58 (2019-08-05), Heft 32, S. 10936-10940 |
Veröffentlichung: | <2004-> : Weinheim : Wiley-VCH ; <i>Original Publication</i>: Weinheim/Bergstr. : New York, : Verlag Chemie ; Academic Press, c1962-, 2019 |
Medientyp: | academicJournal |
ISSN: | 1521-3773 (electronic) |
DOI: | 10.1002/anie.201904672 |
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