DFT Mechanistic Investigation into Ni(II)-Catalyzed Hydroxylation of Benzene to Phenol by H2O2

Introduction of oxygen into aromatic C–H bonds is intriguing from both fundamental and practical perspectives. Although the 3d metal-catalyzed hydroxylation of arenes by H2O2 has been developed by several prominent researchers, a definitive mechanism for these crucial transformations remains elusive. Herein, density functional theory calculations were used to shed light on the mechanism of the established hydroxylation reaction of benzene with H2O2, catalyzed by [NiII(tepa)]2+ (tepa = tris[2-(pyridin-2-yl)ethyl]amine). Dinickel(III) bis(μ-oxo) species have been proposed as the key intermediate responsible for the benzene hydroxylation reaction. Our findings indicate that while the dinickel dioxygen species can be generated as a stable structure, it cannot serve as an active catalyst in this transformation. The calculations allowed us to unveil an unprecedented mechanism composed of six main steps as follows: (i) deprotonation of coordinated H2O2, (ii) oxidative addition, (iii) water elimination, (iv) benzene addition, (v) ketone generation, and (vi) tautomerization and regeneration of the active catalyst. Addition of benzene to oxygen, which occurs via a radical mechanism, turns out to be the rate-determining step in the overall reaction. This study demonstrates the critical role of Ni-oxyl species in such transformations, highlighting how the unpaired spin density value on oxygen and positive charges on the Ni–O• complex affect the activation barrier for benzene addition.