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

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

Wiley-VCH Verlag

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Holze, Patrick
Corona Prieto, Teresa
Frank, Nicolas
Brau-Cula, Beatrice
Herwig, Christian
Company Casadevall, Anna
Limberg, Christian
Date: 2017 February 20
Abstract: 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
Format: application/pdf
Document access: http://hdl.handle.net/10256/13703
Language: eng
Publisher: Wiley-VCH Verlag
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.201609526
info:eu-repo/semantics/altIdentifier/issn/1433-7851
info:eu-repo/semantics/altIdentifier/eissn/1521-3773
info:eu-repo/grantAgreement/MINECO//CTQ2013-43012-P/ES/INVESTIGACIONES MECANISTICAS PARA SINTESIS ORGANICA SOSTENIBLE VIA ACTIVACION DE PEQUEÑAS MOLECULAS GASEOSAS Y DE ENLACES C-H CON METALES DE LA PRIMERA SERIE DE TRANSICION/
info:eu-repo/grantAgreement/EC/FP7/303522/EU/Key insights into oxidation chemistry through synthetic systems: N2O activation with first-row transition-metals and O2 activation in heterobimetallic Fe-Ni systems/NEWOXMET
Rights: Tots els drets reservats
Subject: Níquel -- Oxidació
Nickel -- Oxidation
Reaccions químiques
Chemical reactions
Catàlisi
Catalysis
Title: Activation of Dioxygen at a Lewis Acidic Nickel(II) Complex: Characterization of a Metastable Organoperoxide Complex
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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