Indirect evidence for a NiIII–oxyl oxidant in the reaction of a NiII complex with peracid

Abstract

The reaction of a Ni^II complex and meta-chloroperoxybenzoic acid (m-CPBA) resulted in the formation of a long-lived Ni^III–chlorobenzoate complex that is a capable hydrocarbon oxidant. Analysis of the post-reaction decay products showed the formation of oxidised derivatives of the supporting ligand (a benzoxazine), and heterolytic O–O bond scission in m-CPBA. This evidence indicates formation of a more potent transient Ni^III–oxyl species, which was further supported by DFT calculations.