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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

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

Wiley-VCH Verlag

Director: Ministerio de Economía y Competitividad (Espanya)
Autor: Holze, Patrick
Corona Prieto, Teresa
Frank, Nicolas
Brau-Cula, Beatrice
Herwig, Christian
Company Casadevall, Anna
Limberg, Christian
Data: 20 febrer 2017
Resum: 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
Cita: 025895
ISSN: 1433-7851 (versió paper)
1521-3773 (versió electrònica)
Accés al document: http://hdl.handle.net/10256/13703
Llenguatge: eng
Editor: Wiley-VCH Verlag
Col·lecció: MINECO/PE 2014-2016/CTQ2013-43012-P
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/anie.201609526
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/303522
És part de: © Angewandte Chemie International Edition, 2017, vol. 56, núm. 9, p. 2307-2311
Drets: Tots els drets reservats
Matèria: Níquel -- Oxidació
Nickel -- Oxidation
Reaccions químiques
Chemical reactions
Catàlisi
Catalysis
Títol: Activation of Dioxygen at a Lewis Acidic Nickel(II) Complex: Characterization of a Metastable Organoperoxide Complex
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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