Activation of Dioxygen at a Lewis Acidic Nickel(II) Complex: Characterization of a Metastable Organoperoxide Complex

In metal-mediated O-2 activation, nickel(II) compounds hardly play a role, but recently it has been shown that enzymes can use nickel(II) for O-2 activation. Now a low-coordinate Lewis acidic nickel(II) complex has been synthesized that reacts with O-2 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-2 activation is proposed to represent a concomitant electron shift from the substrate/co-ligand.