RT Journal Article
T1 A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies
A1 Vilella, Laia
A1 Conde Alcántara, Ana Isabel
A1 Ballcells, David
A1 Díaz Requejo, María Mar
A1 Lledós, Agustín
A1 Pérez Romero, Pedro José
K1 Hydroxylation
AB A dual mechanism for direct benzene catalytic hydroxylation is described. Experimental studies and DFT 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-oxyl intermediate that may interact with the arene ring following two different, competitive routes: (a) electrophilic aromatic substitution, with the copper-oxyl 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 to different extents, the electrophilic substitution route seeming to be largely favoured.
PB Royal Society of Chemistry
SN 2041-6520
SN 2041-6539 (electrónica)
YR 2017
FD 2017
LK http://hdl.handle.net/10272/15234
UL http://hdl.handle.net/10272/15234
LA eng
NO Vilella, L., Conde, A., Balcells, D., Díaz-Requejo, M. M., Lledós, A., & Pérez, P. J. (2017). A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies. Chemical Science, 8(12), 8373-8383. https://doi.org/10.1039/c7sc02898a
NO We thank MINECO for Grants CTQ2014-52769-C3-1-R andCTQ2014-54071-P and COST Action CARISMA CM1205. D. B.acknowledges the support from the Norwegian ResearchCouncil through the Centre of Excellence for Theoretical andComputational Chemistry (CTCC; grant No. 179568/V30), theNorwegian Metacenter for Computational Science (NOTUR;grant nn4654k) and the EU Research Executive Agency fora Marie Curie Fellowship (grant CompuWOC/618303). We alsothank CATEDRA CEPSA-UHU for nancial support.
DS Repositorio Institucional de la Universidad de Huelva
RD 14 jul 2026