Mechanistic Studies on the Reaction between R2N-NONOates and Aquacobalamin: Evidence for Direct Transfer of a Nitroxyl Group from R2N-NONOates to Cobalt(III) Centers

Tales of the unexpected: Transfer of a nitroxyl group from R2N‐NONOates to aquacobalamin to form nitroxylcobalamin does not proceed via H+‐catalyzed R2N‐NONOate decomposition, but instead occurs via a probable NONOate‐cobalamin intermediate (see scheme; r.d.s.=rate‐determining step).

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Bibliographische Detailangaben
Veröffentlicht in:	Angewandte Chemie International Edition 2009-01, Vol.48 (47), p.8909-8913
Hauptverfasser:	Hassanin, Hanaa A., Hannibal, Luciana, Jacobsen, Donald W., El-Shahat, Mohamed F., Hamza, Mohamed S. A., Brasch, Nicola E.
Format:	Artikel
Sprache:	eng
Schlagworte:	Alkenes - chemistry Catalysis cobalamins Cobalt - chemistry Hydrazines - chemistry Kinetics Magnetic Resonance Spectroscopy N,O ligands Nitric Oxide Donors - chemistry Nitrogen Oxides - chemistry Nitroso Compounds - chemistry nitroxyl complexes O ligands Spectrophotometry, Ultraviolet Vitamin B 12 - analogs & derivatives Vitamin B 12 - chemistry vitamins
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Beschreibung
Zusammenfassung:	Tales of the unexpected: Transfer of a nitroxyl group from R2N‐NONOates to aquacobalamin to form nitroxylcobalamin does not proceed via H+‐catalyzed R2N‐NONOate decomposition, but instead occurs via a probable NONOate‐cobalamin intermediate (see scheme; r.d.s.=rate‐determining step).
ISSN:	1433-7851 1521-3773
DOI:	10.1002/anie.200904360