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Rhodium (Thiophosphinoyl)(trimethylsilyl)methanide and Bis(thiophosphinoyl)methanide Complexes: S~S vs. C~S Coordination†

  1. Hadrien Heuclin,
  2. Sophie Carenco,
  3. Xavier-Frédéric Le Goff,
  4. Nicolas Mézailles

Article first published online: 27 JAN 2012

DOI: 10.1002/ejic.201101073

Additional Information

How to Cite

Heuclin, H., Carenco, S., Le Goff, X.-F. and Mézailles, N. (2012), Rhodium (Thiophosphinoyl)(trimethylsilyl)methanide and Bis(thiophosphinoyl)methanide Complexes: S~S vs. C~S Coordination. European Journal of Inorganic Chemistry. doi: 10.1002/ejic.201101073

Author Information

  1. Laboratoire “Hétéroéléments et Coordination”, Ecole Polytechnique, CNRS, 91128 Palaiseau Cedex, France

  1. †

    Dedicated to the memory of our friend and colleague Pascal Le Floch

Publication History

  1. Article first published online: 27 JAN 2012
  2. Manuscript Received: 7 OCT 2011

Funded by

  • Centre National de la Recherche Scientifique (CNRS)
  • Ecole Polytechnique
  • Ecole Polytechnique
  • Direction Générale de l'Armement (DGA)

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Keywords:

  • Rhodium;
  • S ligands;
  • Bidentate ligand;
  • Anions;
  • Density functional calculations;
  • NBO analysis

Graphical Abstract

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The reactions of mono and bis(thiophosphinoyl)methanides with an RhI precursor yielded tetracoordinate RhI complexes in which different coordination modes of the ligands have been observed.

Abstract

A comparative study of the coordination modes of a (thiophosphinoyl)(trimethylsilyl)methanide (1–·Li+) and bis(thiophosphinoyl)methanide (2–·Li+) ligand with RhI was carried out. Several complexes were synthesized and characterized. For 1–·Li+, C~S coordination is forced, whereas for 2–·Li+, S~S and C~S coordination can be achieved. In one case, a dynamic equilibrium between these two modes of coordination was observed. DFT calculations were carried out to rationalize this phenomenon and the stability of the methanide compounds.

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