000130965 001__ 130965 000130965 005__ 20240202151703.0 000130965 0247_ $$2doi$$a10.1002/anie.201808840 000130965 0248_ $$2sideral$$a116302 000130965 037__ $$aART-2019-116302 000130965 041__ $$aeng 000130965 100__ $$0(orcid)0000-0003-0094-0644$$adel Río M.P. 000130965 245__ $$aActivating a Peroxo Ligand for C-O Bond Formation 000130965 260__ $$c2019 000130965 5060_ $$aAccess copy available to the general public$$fUnrestricted 000130965 5203_ $$aDioxygen activation for effective C-O bond formation in the coordination sphere of a metal is a long-standing challenge in chemistry for which the design of catalysts for oxygenations is slowed down by the complicated, and sometimes poorly understood, mechanistic panorama. In this context, olefin–peroxide complexes could be valuable models for the study of such reactions. Herein, we showcase the isolation of rare “Ir(cod)(peroxide)” complexes (cod=1, 5-cyclooctadiene) from reactions with oxygen, and then the activation of the peroxide ligand for O-O bond cleavage and C-O bond formation by transfer of a hydrogen atom through proton transfer/electron transfer reactions to give 2-iradaoxetane complexes and water. 2, 4, 6-Trimethylphenol, 1, 4-hydroquinone, and 1, 4-cyclohexadiene were used as hydrogen atom donors. These reactions can be key steps in the oxy-functionalization of olefins with oxygen, and they constitute a novel mechanistic pathway for iridium, whose full reaction profile is supported by DFT calculations. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 000130965 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FEDER/E08-17R$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-53033-P$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-83421-P$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-87889-P$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-89132-P 000130965 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/ 000130965 590__ $$a12.959$$b2019 000130965 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b15 / 176 = 0.085$$c2019$$dQ1$$eT1 000130965 592__ $$a5.438$$b2019 000130965 593__ $$aChemistry (miscellaneous)$$c2019$$dQ1 000130965 593__ $$aCatalysis$$c2019$$dQ1 000130965 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion 000130965 700__ $$0(orcid)0000-0003-2296-5682$$aAbril P. 000130965 700__ $$0(orcid)0000-0003-4500-1974$$aLópez J.A.$$uUniversidad de Zaragoza 000130965 700__ $$aSodupe M. 000130965 700__ $$aLledós A. 000130965 700__ $$0(orcid)0000-0002-7188-8014$$aCiriano M.A. 000130965 700__ $$0(orcid)0000-0003-3306-0635$$aTejel C.$$uUniversidad de Zaragoza 000130965 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica 000130965 773__ $$g58, 10 (2019), 3037-3041$$pAngew. Chem. (Int. ed.)$$tANGEWANDTE CHEMIE-INTERNATIONAL EDITION$$x1433-7851 000130965 8564_ $$s302655$$uhttps://zaguan.unizar.es/record/130965/files/texto_completo.pdf$$yPostprint 000130965 8564_ $$s3080917$$uhttps://zaguan.unizar.es/record/130965/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint 000130965 909CO $$ooai:zaguan.unizar.es:130965$$particulos$$pdriver 000130965 951__ $$a2024-02-02-14:49:45 000130965 980__ $$aARTICLE