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- Title
Activation of Dioxygen at a Lewis Acidic Nickel(II) Complex: Characterization of a Metastable Organoperoxide Complex.
- Authors
Holze, Patrick; Corona, Teresa; Frank, Nicolas; Braun‐Cula, Beatrice; Herwig, Christian; Company, Anna; Limberg, Christian
- 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.
- Subjects
ACTIVATION (Chemistry); LEWIS acids; DIOXYGENASES; NICKEL compounds; OXYGEN atom transfer reactions; ENZYMES; ATOMIC absorption spectroscopy
- Publication
Angewandte Chemie International Edition, 2017, Vol 56, Issue 9, p2307
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201609526