Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species.
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 (HmCPBA). This compound is only detectable at temperatures below 250 K and is much more reactive toward organic substrates (i.e., C-H bonds, C=C bonds, and sulfides) than previously reported well-defined nickel-oxygen species. Remarkably, this species is formed by heterolytic O-O bond cleavage of a Ni-HmCPBA 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.
['Corona|Teresa|T|', 'Pfaff|Florian F|FF|', 'Acuña-Parés|Ferran|F|', 'Draksharapu|Apparao|A|', 'Whiteoak|Christopher J|CJ|', 'Martin-Diaconescu|Vlad|V|', 'Lloret-Fillol|Julio|J|', 'Browne|Wesley R|WR|', 'Ray|Kallol|K|', 'Company|Anna|A|']
oxidation high-valent metal species nickel reactive intermediates redox chemistry