Activation of Dioxygen at a Lewis Acidic Nickel(II) Complex: Characterization of a Metastable Organoperoxide Complex. Issue 9 (23rd January 2017)

• Record Type: Journal Article
• Authors: Holze, Patrick; Corona, Teresa; Frank, Nicolas; Braun‐Cula, Beatrice; Herwig, Christian; Company, Anna; Limberg, Christian
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 9(2017)
• Page Start: 2307
• Page End: 2311
• Publication Date: 2017-01-23
• Subjects: dioxygen activation -- nickel -- oxidation -- oxygenases -- peroxide; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201609526
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: In metal‐mediated O2 activation, nickel(II) compounds hardly play a role, but recently it has been shown that enzymes can use nickel(II) for O2 activation. Now a low‐coordinate Lewis acidic nickel(II) complex has been synthesized that reacts with O2 to 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 O2 activation is proposed to represent a concomitant electron shift from the substrate/co‐ligand. Abstract : Nickel(II) can do it too : O2 activation can occur even at low temperature if nickel(II) cooperates with a redox‐active ligand, as recently also suggested for the nickel‐dependent quercitinase. First precedence is provided that a nickel(II)organoperoxo moiety can be generated when setting out from a nickel(II) complex and O2 (partial structure of crystallized metastable peroxide shown).