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A competing, dual mechanism for the catalytic direct benzene hydroxylation from combined experimental -DFT studies

Abstract

A dual mechanism for the direct benzene catalytic hydroxylation is described. Experimental studies and DTF calculations have provided a mechanistic explanation for the acid-free, TpxCu-catalyzed hydroxylation of benzene with hydrogen peroxide (Tpx= hydrotrispyrazolylborate ligand). In contrast with other catalytic systems that promote this transformation through Fenton-like pathways, this system operates through a copper-oxo intermediate that may interact with the arene ring following two different, competitive routes: (a) the electrophilic aromatic substitution, with the copper-oxo species acting as the formal electrophile, and (b) the so-called rebound mechanism, in which the hydrogen is abstracted by the Cu-O moiety prior to the C-O bond formation. Both pathways contribute to the global transformation albeit at different extent, the electrophilic substitution route seeming largely favoured.

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Publication details

The article was received on 30 Jun 2017, accepted on 04 Oct 2017 and first published on 05 Oct 2017


Article type: Edge Article
DOI: 10.1039/C7SC02898A
Citation: Chem. Sci., 2017, Accepted Manuscript
  • Open access: Creative Commons BY license
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    A competing, dual mechanism for the catalytic direct benzene hydroxylation from combined experimental -DFT studies

    P. J. Perez, A. I. Conde, L. Vilella, M. M. Diaz-Requejo, A. Lledos and D. Balcells, Chem. Sci., 2017, Accepted Manuscript , DOI: 10.1039/C7SC02898A

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