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Reactivity of a Nickel(II) Bis(amidate) Complex with meta ‐Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species
Author(s) -
Corona Teresa,
Pfaff Florian F.,
AcuñaParés Ferran,
Draksharapu Apparao,
Whiteoak Christopher J.,
MartinDiaconescu Vlad,
LloretFillol Julio,
Browne Wesley R.,
Ray Kallol,
Company Anna
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201501841
Subject(s) - heterolysis , oxidizing agent , nickel , reactivity (psychology) , chemistry , reactive oxygen species , reactive intermediate , ligand (biochemistry) , bond cleavage , medicinal chemistry , stereochemistry , organic chemistry , catalysis , medicine , biochemistry , alternative medicine , receptor , pathology
Herein, we report the formation of a highly reactive nickel–oxygen species that has been trapped following reaction of a Ni II precursor bearing a macrocyclic bis(amidate) ligand with meta‐ chloroperbenzoic acid (H m CPBA). This compound is only detectable at temperatures below 250 K and is much more reactive toward organic substrates (i.e., CH bonds, CC bonds, and sulfides) than previously reported well‐defined nickel–oxygen species. Remarkably, this species is formed by heterolytic OO bond cleavage of a Ni–H m CPBA precursor, which is concluded from experimental and computational data. On the basis of spectroscopy and DFT calculations, this reactive species is proposed to be a Ni III –oxyl compound.