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Activation of Dioxygen at a Lewis Acidic Nickel(II) Complex: Characterization of a Metastable Organoperoxide Complex
Author(s) -
Holze Patrick,
Corona Teresa,
Frank Nicolas,
BraunCula Beatrice,
Herwig Christian,
Company Anna,
Limberg Christian
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201609526
Subject(s) - nickel , chemistry , hydrogen peroxide , photochemistry , hydrogen atom abstraction , metal , peroxide , lewis acids and bases , ligand (biochemistry) , reactive intermediate , substrate (aquarium) , radical , inorganic chemistry , catalysis , organic chemistry , biochemistry , oceanography , receptor , geology
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.