Activating a Peroxo Ligand for C-O Bond Formation

Autor: Paula Abril, Miguel A. Ciriano, M. Pilar del Río, Mariona Sodupe, José A. López, Agustí Lledós, Cristina Tejel
Přispěvatelé: Agencia Estatal de Investigación (España), Ministerio de Economía, Industria y Competitividad (España), Ministerio de Economía y Competitividad (España), European Commission, Gobierno de Aragón
Rok vydání: 2018
Předmět:
Zdroj: Digital.CSIC. Repositorio Institucional del CSIC
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ISSN: 1521-3773
Popis: 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.
Generous financial support from MINECO/FEDER (Projects CTQ2014‐53033‐P and CTQ2017‐83421‐P to C.T.; CTQ2017‐87889‐P to A.L.; and CTQ2017‐89132‐P to M.S.) and Gobierno de Aragón (GA/FEDER, Inorganic Molecular Architecture Group E08_17R to C.T.) is gratefully acknowledged. M.P.d.R. and P.A. thank MINECO/FEDER for a JdC contract and a FPI fellowship, respectively.
Databáze: OpenAIRE
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