CORONA, Teresa, PFAFF, Florian F., ACUÑA-PARÉS, Ferran, DRAKSHARAPU, Apparao, WHITEOAK, Christopher, MARTIN-DIACONESCU, Vlad, LLORET-FILLOL, Julio, BROWNE, Wesley R., RAY, Kallol and COMPANY, Anna (2015). Reactivity of a Nickel(II) Bis(amidate) Complex withmeta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species. Chemistry : A European Journal, 21 (42), 15029-15038.
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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., C[BOND]H bonds, C[DOUBLE BOND]C bonds, and sulfides) than previously reported well-defined nickel–oxygen species. Remarkably, this species is formed by heterolytic O[BOND]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 NiIII–oxyl compound.
|Depositing User:||Christopher Whiteoak|
|Date Deposited:||04 Apr 2016 13:38|
|Last Modified:||08 Dec 2016 17:36|
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