DUGi

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

http://dugi.udg.edu/item/http:@@@@hdl.handle.net@@10256@@13703

Aquest mateix article està publicat a l’edició alemanya d’’Angewandte Chemie’ (ISSN 0044-8249, EISSN 1521-3757), 2017, vol.129, núm.9, p. 2347–2351. DOI http://dx.doi.org/10.1002/ange.201609526

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

We are thankful to the European Commission (FP7-PEOPLE-2011-CIG-303522 to A.C.) and the MINECO of Spain (CTQ2013-43012-P and RYC-2011–08683 to A.C.) for financial support

© Angewandte Chemie International Edition, 2017, vol. 56, núm. 9, p. 2307-2311

Wiley-VCH Verlag