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Complete σ* intramolecular aromatic hydroxylation mechanism through O2 activation by a Schiff base macrocyclic dicopper (I) complex

In this work we analyze the whole molecular mechanism for intramolecular aromatic hydroxylation through O2 activation by a Schiff hexaazamacrocyclic dicopper(I) complex, [CuI2(bsH2m)]2+. Assisted by DFT calculations, we unravel the reaction pathway for the overall intramolecular aromatic hydroxylation, i.e., from the initial O2 reaction with the dicopper(I) species to first form a CuICuII-superoxo species, the subsequent reaction with the second CuI center to form a μ-η2:η2-peroxo-CuII 2 intermediate, the concerted peroxide O–O bond cleavage and C–O bond formation, followed finally by a proton transfer to an alpha aromatic carbon that immediately yields the product [CuII 2(bsH2m-O)(μ-OH)]2+

Beilstein Journal of Organic Chemistry, 2013, núm. 9, p. 585-593

Beilstein-Institut

Autor: Poater Teixidor, Albert
Solà i Puig, Miquel
Data: 2013
Resum: In this work we analyze the whole molecular mechanism for intramolecular aromatic hydroxylation through O2 activation by a Schiff hexaazamacrocyclic dicopper(I) complex, [CuI2(bsH2m)]2+. Assisted by DFT calculations, we unravel the reaction pathway for the overall intramolecular aromatic hydroxylation, i.e., from the initial O2 reaction with the dicopper(I) species to first form a CuICuII-superoxo species, the subsequent reaction with the second CuI center to form a μ-η2:η2-peroxo-CuII 2 intermediate, the concerted peroxide O–O bond cleavage and C–O bond formation, followed finally by a proton transfer to an alpha aromatic carbon that immediately yields the product [CuII 2(bsH2m-O)(μ-OH)]2+
Format: application/pdf
ISSN: 1860-5397
Accés al document: http://hdl.handle.net/10256/8382
Llenguatge: eng
Editor: Beilstein-Institut
Col·lecció: MICINN/PN 2012-2015/RYC-2009-05226
MICINN/PN 2012-2014/CTQ2011-23156
AGAUR/2009-2014/2009 SGR-637
AGAUR/2011BE100793
Reproducció digital del document publicat a: http://dx.doi.org/10.3762/bjoc.9.63
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
És part de: Beilstein Journal of Organic Chemistry, 2013, núm. 9, p. 585-593
Drets: Attribution 3.0 Spain
URI Drets: http://creativecommons.org/licenses/by/3.0/es/
Matèria: Compostos aromàtics
Aromatic compounds
Enllaços químics
Chemical bonds
Química quàntica
Quantum chemistry
Títol: Complete σ* intramolecular aromatic hydroxylation mechanism through O2 activation by a Schiff base macrocyclic dicopper (I) complex
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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