title: Activation of Dioxygen at a Lewis Acidic Nickel(II) Complex: Characterization of a Metastable Organoperoxide Complex.
abstract: In metal-mediated O2activation, nickel(II) compounds hardly play a role, but recently it has been shown that enzymes can use nickel(II) for O2activation. Now a low-coordinate Lewis acidic nickel(II) complex has been synthesized that reacts with O2to give a nickel(II) organoperoxide, as proposed for the enzymatic system. Its formation was studied further by UV/Vis absorption spectroscopy, leading to the observation of a short-lived intermediate that proved to be reactive in both oxygen atom transfer and hydrogen abstraction reactions, while the peroxide efficiently transfers O atoms. Both for the enzyme and for the functional model, the key to O2activation is proposed to represent a concomitant electron shift from the substrate/co-ligand.
authors.affiliation: Humboldt-Universität zu Berlin, Institut für Chemie, Brook-Taylor-Strasse 2, 12489, Berlin, Germany.
authors.forename: Patrick
authors.initials: P
authors.lastname: Holze
authors.affiliation: Grup de Química Bioinspirada, Supramolecular i Catàlisi (QBIS-CAT), Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, 17003, Girona, Catalonia, Spain.
authors.forename: Teresa
authors.identifier: 0000-0001-8033-8180
authors.initials: T
authors.lastname: Corona
authors.affiliation: Humboldt-Universität zu Berlin, Institut für Chemie, Brook-Taylor-Strasse 2, 12489, Berlin, Germany.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Frank
authors.affiliation: Humboldt-Universität zu Berlin, Institut für Chemie, Brook-Taylor-Strasse 2, 12489, Berlin, Germany.
authors.forename: Beatrice
authors.initials: B
authors.lastname: Braun-Cula
authors.affiliation: Humboldt-Universität zu Berlin, Institut für Chemie, Brook-Taylor-Strasse 2, 12489, Berlin, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Herwig
authors.affiliation: Grup de Química Bioinspirada, Supramolecular i Catàlisi (QBIS-CAT), Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, 17003, Girona, Catalonia, Spain.
authors.forename: Anna
authors.identifier: 0000-0003-4845-4418
authors.initials: A
authors.lastname: Company
authors.affiliation: Humboldt-Universität zu Berlin, Institut für Chemie, Brook-Taylor-Strasse 2, 12489, Berlin, Germany.
authors.forename: Christian
authors.identifier: 0000-0002-0751-1386
authors.initials: C
authors.lastname: Limberg
keywords: dioxygen activation; nickel; oxidation; oxygenases; peroxide