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

ABSTRACT: A dual mechanism for direct benzene catalytic hydroxylation is described. Experimental studies and DFT calculations have provided a mechanistic explanation for the acid-free, Tp ^x Cu-catalyzed hydroxylation of benzene with hydrogen peroxide (Tp ^x = 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

SUBMITTER: Vilella L 

PROVIDER: S-EPMC5863614 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature