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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Bibliographic Details
Published in:Angewandte Chemie International Edition 2009-01, Vol.48 (47), p.8909-8913
Main Authors: Hassanin, Hanaa A., Hannibal, Luciana, Jacobsen, Donald W., El-Shahat, Mohamed F., Hamza, Mohamed S. A., Brasch, Nicola E.
Format: Article
Language:English
Subjects:
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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Summary: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