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Activation of Dioxygen at a Lewis Acidic Nickel(II) Complex: Characterization of a Metastable Organoperoxide Complex. | LitMetric
In metal-mediated O activation, nickel(II) compounds hardly play a role, but recently it has been shown that enzymes can use nickel(II) for O activation. Now a low-coordinate Lewis acidic nickel(II) complex has been synthesized that reacts with O 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 O activation is proposed to represent a concomitant electron shift from the substrate/co-ligand.
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