Carbene-Stabilized Phosphenium Oxides and Sulfides

Authors

  • Carine Maaliki,

    1. CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, F-31077 Toulouse (France), Fax: (+33) 561-55-30-03
    2. Université de Toulouse, UPS, INP, LCC, F-31077 Toulouse (France)
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  • Dr. Christine Lepetit,

    1. CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, F-31077 Toulouse (France), Fax: (+33) 561-55-30-03
    2. Université de Toulouse, UPS, INP, LCC, F-31077 Toulouse (France)
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  • Carine Duhayon,

    1. CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, F-31077 Toulouse (France), Fax: (+33) 561-55-30-03
    2. Université de Toulouse, UPS, INP, LCC, F-31077 Toulouse (France)
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  • Dr. Yves Canac,

    Corresponding author
    1. CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, F-31077 Toulouse (France), Fax: (+33) 561-55-30-03
    2. Université de Toulouse, UPS, INP, LCC, F-31077 Toulouse (France)
    • CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, F-31077 Toulouse (France), Fax: (+33) 561-55-30-03
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  • Prof. Remi Chauvin

    Corresponding author
    1. CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, F-31077 Toulouse (France), Fax: (+33) 561-55-30-03
    2. Université de Toulouse, UPS, INP, LCC, F-31077 Toulouse (France)
    • CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, F-31077 Toulouse (France), Fax: (+33) 561-55-30-03
    Search for more papers by this author

Abstract

Carbene→chalcogenophosphenium adducts, which correspond to an intermolecular stabilization mode of the so far elusive, free oxo- and thiooxophosphenium species [R2P+=X] (X=O, S) by imidazolylidene (NHC) and diaminocyclopropenylidene (BAC) donors, have been isolated and fully characterized. The dative character of the R2C:→P+(X)Ph2 bond was confirmed experimentally by nucleophilic displacement of the carbene donor with a chloride ion and by an exchange reaction of the NHC ligand of the NHC:→P+(O)Ph2 adduct with an independently prepared BAC ligand, thereby giving the BAC:→P+(O)Ph2 adduct. This dative character was further characterized by the DFT-calculated preference of carbene→chalcogenophosphenium systems for a heterolytic dissociation mode over a homolytic one.

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