Rhodium Complexes Promoting C−O Bond Formation in Reactions with Oxygen: The Role of Superoxo Species

Laia Vilella-Arribas, Max García-Melchor, David Balcells, Agustí Lledós, José A. López, Sofía Sancho, B. Eva Villarroya, M. Pilar del Río, Miguel A. Ciriano, Cristina Tejel

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5 Citations (Scopus)


© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim C−O bond formation in reactions of olefins with oxygen is a long standing challenge in chemistry for which the very complicated—sometimes controversial—mechanistic panorama slows down the design of catalysts for oxygenations. In this regard, the mechanistic details of the oxidation of the complex [Rh(cod)(Ph2N3)] (1) (cod=1,5-cyclooctadiene) with oxygen to the unique 2-rhodaoxetane compound [{Rh(OC8H12)(Ph2N3)}2] (2) has been investigated by DFT calculations. The results of this study provide evidences for a novel bimetallic mechanism in which two rhodium atoms redistribute the four electrons involved in the cleavage of the O=O bond. Furthermore, both oxygen atoms are used to create two new C−O bonds in a controlled fashion with 100 % atom economy. The key intermediates that we have found in this process are a mononuclear open-shell triplet superoxo compound, an open-shell singlet “μ-(peroxo)” derivative, and a closed-shell singlet “bis(μ-oxo)” complex. Some of the findings are used to predict the reactions of RhI complexes with oxygen, exemplified by that of the complex [Rh(cod)(OnapyMe2)] (3). Starting from 3, [{Rh(OC8H12)(OnapyMe2)}2] (4) has been prepared and characterized, which represents the second example of a 2-rhodaoxetane compound coming from an oxygenation reaction with oxygen.
Original languageEnglish
Pages (from-to)5232-5243
JournalChemistry - A European Journal
Issue number22
Publication statusPublished - 1 Jan 2017


  • C−O bond formation
  • density functional calculations
  • dioxygen cleavage
  • rhodaoxetanes
  • rhodium


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