Theoretical Exploration of the Oxidative Properties of a [(trenMe1)CuO2]+ Adduct Relevant to Copper Monooxygenase Enzymes: Insights into Competitive Dehydrogenation versus Hydroxylation Reaction Pathways
Impact
Scholar |
Other documents of the author: de la LANDE, Aurélien; Parisel, Olivier; Gérard, Hélène; Moliner, Vicent; Reinaud, Olivia
Metadata
Show full item recordcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
comunitat-uji-handle4:
INVESTIGACIONThis resource is restricted
http://dx.doi.org/10.1002/chem.200701595 |
Metadata
Title
Theoretical Exploration of the Oxidative Properties of a [(trenMe1)CuO2]+ Adduct Relevant to Copper Monooxygenase Enzymes: Insights into Competitive Dehydrogenation versus Hydroxylation Reaction PathwaysAuthor (s)
Date
2008-07Publisher
WileyISSN
0947-6539Bibliographic citation
Chemistry - A European Journal, 14, 21, p. 6465–6473Type
info:eu-repo/semantics/articlePublisher version
http://onlinelibrary.wiley.com/doi/10.1002/chem.200701595/fullVersion
info:eu-repo/semantics/publishedVersionSubject
Abstract
Singlet and triplet H-transfer reaction paths from CH and NH bonds were examined by means of DFT and spin-flip TD-DFT computations on the [(trenMe1)CuO2]+ adduct. The singlet energy surfaces allow its evolution towards ... [+]
Singlet and triplet H-transfer reaction paths from CH and NH bonds were examined by means of DFT and spin-flip TD-DFT computations on the [(trenMe1)CuO2]+ adduct. The singlet energy surfaces allow its evolution towards H2O2 and an imine species. Whereas NH cleavage appears to be a radical process, CH rupture results in a carbocation intermediate stabilized by an adjacent N atom and an electrostatic interaction with the [CuIOOH] metal core. Upon injection of an additional electron, the latter species straightforwardly forms a hydroxylated product. Based on these computational results, a new mechanistic description of the reactivity of copper monooxygenases is proposed. [-]
Rights
Copyright © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/restrictedAccess
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/restrictedAccess
This item appears in the folowing collection(s)
- QFA_Articles [825]