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 inAngewandte Chemie International Edition Vol. 48; no. 47; pp. 8909 - 8913
Main Authors Hassanin, Hanaa A., Hannibal, Luciana, Jacobsen, Donald W., El-Shahat, Mohamed F., Hamza, Mohamed S. A., Brasch, Nicola E.
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 01.01.2009
WILEY‐VCH Verlag
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).
Bibliography:We thank Prof. Rudi van Eldik, University of Erlangen-Nürnberg (Germany) and Prof. István Fábián, University of Debrecen, Hungary for useful discussions. This research was funded by the Egyptian Ministry of Higher Education (PhD scholarship to H.A.H.), and the NSF (CHE-0848397, N.E.B.). R2N-NONOates=1-(N,N-dialkylamino)diazen-1-ium-1,2-diolates, nitroxyl=NO−.
ark:/67375/WNG-NNWB5352-7
ArticleID:ANIE200904360
istex:81B837EC6C108B7E6E183EF699A9440FEEB2BE0A
NSF - No. CHE-0848397
2
−
We thank Prof. Rudi van Eldik, University of Erlangen‐Nürnberg (Germany) and Prof. István Fábián, University of Debrecen, Hungary for useful discussions. This research was funded by the Egyptian Ministry of Higher Education (PhD scholarship to H.A.H.), and the NSF (CHE‐0848397, N.E.B.). R
N‐NONOates=1
,
N
dialkylamino)diazen‐1‐ium‐1,2‐diolates, nitroxyl=NO
.
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
nbrasch@kent.edu
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.200904360