Reductive NO Coupling at Dicopper Center via a [Cu 2 (NO) 2 ] 2+ Diamond-Core Intermediate.

Autor: Tao W; Department of Chemistry & Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States., Carter S; Department of Chemistry & Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States., Trevino R; Department of Chemistry & Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States., Zhang W; Department of Chemistry & Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States., Shafaat HS; Department of Chemistry & Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States., Zhang S; Department of Chemistry & Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2022 Dec 14; Vol. 144 (49), pp. 22633-22640. Date of Electronic Publication: 2022 Dec 05.
DOI: 10.1021/jacs.2c09523
Abstrakt: Treatment of a dicopper(I,I) complex with excess amounts of NO leads to the formation of a dicopper dinitrosyl [Cu 2 (NO) 2 ] 2+ complex capable of (i) releasing two equivalents of NO reversibly in 90% yield and (ii) reacting with another equivalent of NO to afford N 2 O and dicopper nitrosyl oxo species [Cu 2 (NO)(O)] 2+ . Resonance Raman characterization of the [Cu 2 (NO) 2 ] 2+ complex shows a 15 N-sensitive N═O stretch at 1527.6 cm -1 and two Cu-N stretches at 390.6 and 414.1 cm -1 , supporting a symmetric diamond-core structure with bis-μ-NO ligands. The conversion of [Cu 2 (NO) 2 ] 2+ to [Cu 2 (NO)O] 2+ occurs via a rate-limiting reaction with NO and bypasses the dicopper oxo intermediate, a mechanism distinct from that of diFe-mediated NO reduction to N 2 O.
Databáze: MEDLINE
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