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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-Institut

Manager: Ministerio de Ciencia e Innovación (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Author: Poater Teixidor, Albert
Solà i Puig, Miquel
Date: 2013
Abstract: 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
Document access: http://hdl.handle.net/10256/8382
Language: eng
Publisher: Beilstein-Institut
Collection: info:eu-repo/semantics/altIdentifier/doi/10.3762/bjoc.9.63
info:eu-repo/semantics/altIdentifier/eissn/1860-5397
info:eu-repo/grantAgreement/MICINN//RYC-2009-05226/ES/RYC-2009-05226/
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/
AGAUR/2009-2014/2009 SGR-637
AGAUR/2011BE100793
info:eu-repo/grantAgreement/EC/FP7/293900/EU/Ab initio Statics and Molecular Dynamics Simulation of Olefin Metathesis Catalysts for pharmacological purposes/COMPUTEDRUG
Rights: Attribution 3.0 Spain
Rights URI: http://creativecommons.org/licenses/by/3.0/es/
Subject: Compostos aromàtics
Aromatic compounds
Enllaços químics
Chemical bonds
Química quàntica
Quantum chemistry
Title: Complete σ* intramolecular aromatic hydroxylation mechanism through O2 activation by a Schiff base macrocyclic dicopper (I) complex
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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