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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 aCuICuII-superoxo species, the subsequent reaction with the second CuI center to form a μ-η2:η2-peroxo-CuII 2 intermediate, theconcerted 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

Author: Poater Teixidor, Albert
Solà i Puig, Miquel
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 aCuICuII-superoxo species, the subsequent reaction with the second CuI center to form a μ-η2:η2-peroxo-CuII 2 intermediate, theconcerted 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+
Document access: http://hdl.handle.net/2072/218106
Language: eng
Publisher: Beilstein-Institut
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: Recercat

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