Reaction of a copper-dioxygen complex with nitrogen monoxide (*NO) leads to a copper(II)-peroxynitrite species.
In: Journal of the American Chemical Society, Jg. 130 (2008-05-28), Heft 21, S. 6700-1
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Zugriff:
A discrete peroxynitrite-copper(II) complex, [(TMG3tren)CuII(-OONO)]+ (3), has been generated in solution (ESI-MS, m/z = 565.15; tetragonal EPR) by reacting *NO(g) with superoxo complex [(TMG3tren)CuII(O2*-)]+ (2). Complex 3 undergoes a thermal transformation to give CuII-nitrite complex [(TMG3tren)CuII(-ONO)]+ (4) (X-ray) along with ca. 0.5 molar equiv dioxygen. A DFT calculation derived structure with cyclic bidentate k2-O,O'-OONO bound peroxynitrite moiety and dx2-y2 ground state is proposed. Experiments using 18O2 suggest that the adjacent peroxo oxygen atoms in 3 are derived from molecular oxygen. Further, 18O2 containing 3 undergoes O-O bond cleavage to form singly 18-O-labeled 4. The results suggest the viability of biological CuI/O2/(*NO) peroxynitrite formation and chemistry, that is, not coming from free superoxide plus *NO reaction.
| Titel: |
Reaction of a copper-dioxygen complex with nitrogen monoxide (*NO) leads to a copper(II)-peroxynitrite species.
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| Autor/in / Beteiligte Person: | Maiti, D ; Lee, DH ; Narducci Sarjeant, AA ; Pau, MY ; Solomon, EI ; Gaoutchenova, K ; Sundermeyer, J ; Karlin, KD |
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| Zeitschrift: | Journal of the American Chemical Society, Jg. 130 (2008-05-28), Heft 21, S. 6700-1 |
| Veröffentlichung: | Washington, DC : American Chemical Society ; <i>Original Publication</i>: Easton, Pa. [etc.], 2008 |
| Medientyp: | academicJournal |
| ISSN: | 1520-5126 (electronic) |
| DOI: | 10.1021/ja801540e |
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