Theoretical study of the hydroxylation of phenolates by the Cu2O2(N,N'-dimethylethylendiamine)22+ complex
dc.contributor.author
dc.date.accessioned
2019-07-10T08:11:21Z
dc.date.available
2019-07-10T08:11:21Z
dc.date.issued
2009-02-01
dc.identifier.issn
0949-8257
dc.identifier.uri
dc.description.abstract
Tyrosinase catalyses the ortho-hydroxylation of monophenol and the subsequent oxidation of the diphenolic product to the resulting quinone. In efforts to create biomimetic copper complexes that can oxidize C-H bonds, Stack and coworkers recently reported a synthetic -2:2-peroxodicopper(II)(DBED)2 complex (DBED = N,N'-di-tert-butylethylendiamine), which rapidly hydroxylates phenolates. A reactive intermediate consistent with a bis--oxo-dicopper(III)-phenolate complex, with the O-O bond fully cleaved, is observed experimentally. Overall, the evidence for sequential O O bond cleavage and C-O bond formation in this synthetic complex suggests an alternative mechanism to the concerted or late stage O-O bond scission generally accepted for the phenol hydroxylation reaction performed by tyrosinase. In this work, the reaction mechanism of this peroxodicopper(II) complex has been studied with hybrid density functional methods by replacing DBED in the -2:2-peroxodicopper(II)(DBED)2 complex by DMED ligands (DMED = N,N'-dimethylethylendiamine) to reduce the computational costs. The reaction mechanism obtained is compared with the existing proposals for the catalytic ortho-hydroxylation of monophenol and the subsequent oxidation of the diphenolic product to the resulting quinone with the aim of gaining some understanding about the copper-promoted oxidation processes mediated by 2:1 Cu(I)O2-derived species
dc.description.sponsorship
Financial help has been furnished by the Spanish Ministerio de Educación y Ciencia
(MEC) projects No. CTQ2005-08797-C02-01/BQU and CTQ2008-03077/BQU and by
the Catalan Departament d’Universitats, Recerca i Societat de la Informació (DURSI) of
the Generalitat de Catalunya project No. 2005SGR-00238
dc.format.extent
14 p.
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application/pdf
dc.language.iso
eng
dc.publisher
Springer-Verlag
dc.relation
MEC/PN 2005-2008/CTQ2005-08797-C02-01
info:eu-repo/grantAgreement/MICINN//CTQ2008-03077/ES/CLUSTERES METALICOS Y SEMIMETALICOS. ESTUDIOS DE AROMATICIDAD Y REACTIVIDAD/
dc.relation.isformatof
Versió postprint del document publicat a: https://doi.org/10.1007/s00775-008-0443-y
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© Journal of Biological Inorganic Chemistry, 2009, vol. 14, núm. 2, p. 229-242
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Articles publicats (D-Q)
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Tots els drets reservats
dc.source
Güell Serra, Mireia Luis Luis, Josep Maria Solà i Puig, Miquel Siegbahn, P. E. M. 2009 Theoretical study of the hydroxylation of phenolates by the Cu2O2(N,N'-dimethylethylendiamine)22+ complex Journal of Biological Inorganic Chemistry 14 2 229 242
dc.title
Theoretical study of the hydroxylation of phenolates by the Cu2O2(N,N'-dimethylethylendiamine)22+ complex
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
010575
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.ProjectAcronym
dc.identifier.eissn
1432-1327