Unraveling the Mechanism of Hydrogen Atom Transfer by a Nickel-Hypochlorite Species and the Influence of Electronic Effects

Abstract

Theoretical calculations show that the active species in C−H hydrogen atom abstraction corresponds to [Ni(O)(HL)]+, formed after homolytic cleavage of the O−Cl bond of the experimentally trapped [Ni(OCl)(HL)]+. Electronic tuning of the macrocyclic ligand has a very modest impact on the reactivity and stability of the corresponding active species, which show a controversial oxidation state assignment due to the redox noninnocence of the ligands, as ascertained by the effective oxidation state analysis