Abstract
The oxidation of hydrocarbons is an important chemical transformation with relevance to biology and industry. Ni-catalyzed transformations are more scarce compared to Mn or Fe but have gained attention in recent years, affording efficient oxidations. Understanding the mechanism of action of these catalysts, including the detection and characterization of the active nickel-oxygen species, is of interest to design better catalysts. In this work, we undertake a theoretical study to unravel the mechanism of formation of the previously reported [Ni(OCl)((H)L)](+) ((H)2) and how it activates C-H bonds. We disclose that the active species is indeed compound [Ni(O)((H)L)](+), formed after homolytic cleavage of the O-Cl bond in (H)2 assisted by a chlorine radical. [Ni(O)((H)L)](+) mediates C-H activation through an asynchronous concerted mechanism, in which the transition state is given by hydrogen atom transfer. Moreover, the electronic tuning of the ligand has a very modest impact on the stability and reactivity of the corresponding (X)2 species. Effective oxidation state analysis reveals an intriguing electronic structure of (H)2 and [Ni(O)((H)L)](+), in which both the macrocycic (H)L ligand and the OCl and O ligands behave as redox noninnocent. Such redox activity leads to a fully ambiguous oxidation state assignation.