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Reactivity of Phosphane–Imidazolium Salts Towards [Ir(COD)Cl]2: Preparation of New Hydridoiridium(III) Complexes Bearing Abnormal Carbenes†

  1. Joffrey Wolf,
  2. Agnès Labande,
  3. Jean-Claude Daran,
  4. Rinaldo Poli

Article first published online: 21 MAY 2008

DOI: 10.1002/ejic.200800270

Issue

European Journal of Inorganic Chemistry

European Journal of Inorganic Chemistry

Volume 2008, Issue 19, pages 3024–3030, July 2008

Additional Information

How to Cite

Wolf, J., Labande, A., Daran, J.-C. and Poli, R. (2008), Reactivity of Phosphane–Imidazolium Salts Towards [Ir(COD)Cl]2: Preparation of New Hydridoiridium(III) Complexes Bearing Abnormal Carbenes. European Journal of Inorganic Chemistry, 2008: 3024–3030. doi: 10.1002/ejic.200800270

Author Information

  1. Laboratoire de Chimie de Coordination, UPR CNRS 8241 (lié par convention à l'Université Paul Sabatier et à l'Institut National Polytechnique de Toulouse), 205 route de Narbonne, 31077 Toulouse Cedex 4, France, Fax: +33-5-61553003

  1. †

    Dedicated to Prof. W. A. Herrmann on the occasion of his 60th birthday

Publication History

  1. Issue published online: 18 JUN 2008
  2. Article first published online: 21 MAY 2008
  3. Manuscript Received: 13 MAR 2008

Funded by

  • Centre National de la Recherche Scientifique (C.N.R.S.)
  • Fonds Social Européen (F.S.E.)

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Keywords:

  • Carbenes;
  • Phosphane ligands;
  • Iridium;
  • Hydrides;
  • C–H activation

Graphical Abstract

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Phosphane–imidazolium salts added to the iridium complex [Ir(COD)(μ-Cl)]2 without the need of a base and led to hydridoiridium(III) complexes containing “abnormal” carbene ligands, through C–H insertion at the C5 position of the imidazolium ring.

Abstract

The unusual reactivity of chelating phosphane–imidazolium salts MesImEtPPh2+Br–, DIPP-ImEtPPh2+Br–, and MesImEtPPh2+BF4– towards the low-oxidation-state iridium complex [Ir(COD)(μ-Cl)]2 was studied. In the absence of a base, the C–H insertion at the C5 position of the imidazolium ring was the only reaction that occurred, with no normal NHC observed, leading to hydridoiridium(III) complexes. This reactivity was independent of the nature of the imidazolium counteranion and of the substitution pattern of the aryl group. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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