Activating a Peroxo Ligand for C−O Bond Formation

M. Pilar del Río, Paula Abril, José A. López, Mariona Sodupe, Agustí Lledós, Miguel A. Ciriano, Cristina Tejel

Research output: Contribution to journalArticleResearch

5 Citations (Scopus)


© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 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.
Original languageEnglish
Pages (from-to)3037-3041
JournalAngewandte Chemie - International Edition
Publication statusPublished - 4 Mar 2019


  • 2-iridaoxetanes
  • dioxygen cleavage
  • iridium
  • oxygenation
  • peroxide complexes


Dive into the research topics of 'Activating a Peroxo Ligand for C−O Bond Formation'. Together they form a unique fingerprint.

Cite this