TY - JOUR
T1 - Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid
T2 - Formation of a Potent Oxidizing Species
AU - Corona, Teresa
AU - Pfaff, Florian F.
AU - Acuña-Parés, Ferran
AU - Draksharapu, Apparao
AU - Whiteoak, Christopher J.
AU - Martin-Diaconescu, Vlad
AU - Lloret-Fillol, Julio
AU - Browne, Wesley R.
AU - Ray, Kallol
AU - Company, Anna
N1 - Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2015/10/1
Y1 - 2015/10/1
N2 - Herein, we report the formation of a highly reactive nickel-oxygen species that has been trapped following reaction of a NiII 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., 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-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 NiIII-oxyl compound. A highly reactive nickel-oxygen species has been spectroscopically trapped after heterolytic OO bond cleavage during the reaction of a NiII precursor with meta-chloroperbenzoic acid (HmCPBA). This species is used to carry out the oxidation of different substrates, such as olefins, sulfides, and CH bonds (see scheme).
AB - Herein, we report the formation of a highly reactive nickel-oxygen species that has been trapped following reaction of a NiII 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., 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-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 NiIII-oxyl compound. A highly reactive nickel-oxygen species has been spectroscopically trapped after heterolytic OO bond cleavage during the reaction of a NiII precursor with meta-chloroperbenzoic acid (HmCPBA). This species is used to carry out the oxidation of different substrates, such as olefins, sulfides, and CH bonds (see scheme).
KW - high-valent metal species
KW - nickel
KW - oxidation
KW - reactive intermediates
KW - redox chemistry
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U2 - 10.1002/chem.201501841
DO - 10.1002/chem.201501841
M3 - Article
C2 - 26311073
AN - SCOPUS:84943816672
SN - 0947-6539
VL - 21
SP - 15029
EP - 15038
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 42
ER -