130965 20240202151703.0 doi 10.1002/anie.201808840 sideral 116302 ART-2019-116302 eng del Río M.P. (orcid)0000-0003-0094-0644 Activating a Peroxo Ligand for C-O Bond Formation 2019 Dioxygen activation for effective C-O bond formation in the coordination sphere of a metal is a long-standing challenge in chemistry for which the design of catalysts for oxygenations is slowed down by the complicated, and sometimes poorly understood, mechanistic panorama. In this context, olefin–peroxide complexes could be valuable models for the study of such reactions. Herein, we showcase the isolation of rare “Ir(cod)(peroxide)” complexes (cod=1, 5-cyclooctadiene) from reactions with oxygen, and then the activation of the peroxide ligand for O-O bond cleavage and C-O bond formation by transfer of a hydrogen atom through proton transfer/electron transfer reactions to give 2-iradaoxetane complexes and water. 2, 4, 6-Trimethylphenol, 1, 4-hydroquinone, and 1, 4-cyclohexadiene were used as hydrogen atom donors. These reactions can be key steps in the oxy-functionalization of olefins with oxygen, and they constitute a novel mechanistic pathway for iridium, whose full reaction profile is supported by DFT calculations. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Access copy available to the general public Unrestricted info:eu-repo/grantAgreement/ES/DGA-FEDER/E08-17R info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-53033-P info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-83421-P info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-87889-P info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-89132-P info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 12.959 2019 CHEMISTRY, MULTIDISCIPLINARY 15 / 176 = 0.085 2019 Q1 T1 5.438 2019 Chemistry (miscellaneous) 2019 Q1 Catalysis 2019 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Abril P. (orcid)0000-0003-2296-5682 López J.A. Universidad de Zaragoza (orcid)0000-0003-4500-1974 Sodupe M. Lledós A. Ciriano M.A. (orcid)0000-0002-7188-8014 Tejel C. Universidad de Zaragoza (orcid)0000-0003-3306-0635 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 58, 10 (2019), 3037-3041 Angew. Chem. (Int. ed.) ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 1433-7851 302655 http://zaguan.unizar.es/record/130965/files/texto_completo.pdf Postprint 3080917 http://zaguan.unizar.es/record/130965/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:130965 articulos driver 2024-02-02-14:49:45 ARTICLE