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

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

Paolo Pirovano,^a Abigail R. Berry,^a Marcel Swart

^bc and Aidan R. McDonald

*^a

Author affiliations

* Corresponding authors

^a School of Chemistry and CRANN/AMBER Nanoscience Institute, Trinity College Dublin, The University of Dublin, College Green, Dublin 2, Ireland
E-mail: aidan.mcdonald@tcd.ie

^b ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain

^c Institut de Química Computacional i Catálisi, Universitat de Girona, Facultat de Ciéncies, Campus Montilivi, 17003 Girona, Spain

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.

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Article information

DOI: https://doi.org/10.1039/C7DT03316H
Article type: Paper
Submitted: 06 Sep 2017
Accepted: 28 Nov 2017
First published: 28 Nov 2017

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Dalton Trans., 2018,47, 246-250

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

P. Pirovano, A. R. Berry, M. Swart and A. R. McDonald, Dalton Trans., 2018, 47, 246 DOI: 10.1039/C7DT03316H

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Dalton Transactions