Volume 21, Issue 42 p. 15029-15038
Full Paper

Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species

Teresa Corona

Teresa Corona

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

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Florian F. Pfaff

Florian F. Pfaff

Humboldt Universität zu Berlin, Department of Chemistry, Brook-Taylor Strasse 2, 12489 Berlin (Germany)

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Ferran Acuña-Parés

Ferran Acuña-Parés

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

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Dr. Apparao Draksharapu

Dr. Apparao Draksharapu

Stratingh Institute for Chemistry, Faculty of Mathematics and Natural Sciences, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands)

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Dr. Christopher J. Whiteoak

Dr. Christopher J. Whiteoak

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

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Dr. Vlad Martin-Diaconescu

Dr. Vlad Martin-Diaconescu

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

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Dr. Julio Lloret-Fillol

Dr. Julio Lloret-Fillol

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)

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Prof. Dr. Wesley R. Browne

Prof. Dr. Wesley R. Browne

Stratingh Institute for Chemistry, Faculty of Mathematics and Natural Sciences, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands)

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Dr. Kallol Ray

Dr. Kallol Ray

Humboldt Universität zu Berlin, Department of Chemistry, Brook-Taylor Strasse 2, 12489 Berlin (Germany)

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Dr. Anna Company

Corresponding Author

Dr. Anna Company

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

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) 972-41-81-50Search for more papers by this author
First published: 25 August 2015
Citations: 81

Graphical Abstract

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).

Abstract

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, CC 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.