Activating a Peroxo Ligand for C-O Bond Formation

del Río M.P. ; Abril P. ; López J.A. (Universidad de Zaragoza) ; Sodupe M. ; Lledós A. ; Ciriano M.A. ; Tejel C. (Universidad de Zaragoza)

Resumen: 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

Idioma: Inglés

DOI: 10.1002/anie.201808840

Año: 2019

Publicado en: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 58, 10 (2019), 3037-3041
ISSN: 1433-7851

Factor impacto JCR: 12.959 (2019)

Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 15 / 176 = 0.085 (2019) - Q1 - T1

Factor impacto SCIMAGO: 5.438 - Chemistry (miscellaneous) (Q1) - Catalysis (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA-FEDER/E08-17R
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-53033-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-83421-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-87889-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-89132-P

Tipo y forma: Artículo (PostPrint)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)