Activation of Dioxygen at a Lewis Acidic Nickel(II) Complex: Characterization of a Metastable Organoperoxide Complex
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- 作者：Dr. Patrick Holze ; Teresa Corona ; Nicolas Frank ; Dr. Beatrice Braun-Cula ; Dr. Christian Herwig ; Dr. Anna Company and Prof. Dr. Christian Limberg
- 刊名：Angewandte Chemie
- 出版年：2017
- 出版时间：February 20, 2017
- 年：2017
- 卷：129
- 期：9
- 页码：2347-2351
- 全文大小：1552K
- ISSN：1521-3757
文摘
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.