title: Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species.
abstract: 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.
authors: Group de Química Bioinorgànica, Supramolecular i Catàlisi (QBIS-CAT), Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona (Spain), Fax: (+34) 972-41-81-50.
authors: Teresa
authors: T
authors: Corona
authors: Humboldt Universität zu Berlin, Department of Chemistry, Brook-Taylor Strasse 2, 12489 Berlin (Germany).
authors: Florian F
authors: FF
authors: Pfaff
authors: Group de Química Bioinorgànica, Supramolecular i Catàlisi (QBIS-CAT), Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona (Spain), Fax: (+34) 972-41-81-50.
authors: Ferran
authors: F
authors: Acuña-Parés
authors: Stratingh Institute for Chemistry, Faculty of Mathematics and Natural Sciences, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands).
authors: Apparao
authors: A
authors: Draksharapu
authors: Group de Química Bioinorgànica, Supramolecular i Catàlisi (QBIS-CAT), Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona (Spain), Fax: (+34) 972-41-81-50.
authors: Christopher J
authors: CJ
authors: Whiteoak
authors: Group de Química Bioinorgànica, Supramolecular i Catàlisi (QBIS-CAT), Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona (Spain), Fax: (+34) 972-41-81-50.
authors: Vlad
authors: V
authors: Martin-Diaconescu
authors: Group de Química Bioinorgànica, Supramolecular i Catàlisi (QBIS-CAT), Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona (Spain), Fax: (+34) 972-41-81-50.|Current address: Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain).
authors: Julio
authors: J
authors: Lloret-Fillol
authors: Stratingh Institute for Chemistry, Faculty of Mathematics and Natural Sciences, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands).
authors: Wesley R
authors: WR
authors: Browne
authors: Humboldt Universität zu Berlin, Department of Chemistry, Brook-Taylor Strasse 2, 12489 Berlin (Germany).
authors: Kallol
authors: K
authors: Ray
authors: Group de Química Bioinorgànica, Supramolecular i Catàlisi (QBIS-CAT), Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona (Spain), Fax: (+34) 972-41-81-50. anna.company@udg.edu.
authors: Anna
authors: A
authors: Company
keywords: high-valent metal species; nickel; oxidation; reactive intermediates; redox chemistry