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

Paolo Pirovano; Abigail R Berry; Marcel Swart; Aidan R McDonald

doi:10.1039/c7dt03316h

Indirect evidence for a Ni^III-oxyl oxidant in the reaction of a Ni^II complex with peracid

Dalton Trans. 2017 Dec 19;47(1):246-250. doi: 10.1039/c7dt03316h.

Authors

Paolo Pirovano¹, Abigail R Berry, Marcel Swart, Aidan R McDonald

Affiliation

¹ School of Chemistry and CRANN/AMBER Nanoscience Institute, Trinity College Dublin, The University of Dublin, College Green, Dublin 2, Ireland. aidan.mcdonald@tcd.ie.

PMID: 29211082
DOI: 10.1039/c7dt03316h

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.