Carbene-Stabilized Phosphenium Oxides and Sulfides

Carine Maaliki (1) , Christine Lepetit (1) , Carine Duhayon (1) , Yves Canac (1) , Remi Chauvin (1)

1 LCC - Laboratoire de chimie de coordination

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.

Mots clés: Carbenes; Dative bonds; Exchange interactions; Phosphenium compounds; Stabilization

Domaines: Chimie de coordination

Carine Maaliki, Christine Lepetit, Carine Duhayon, Yves Canac, Remi Chauvin. Carbene-Stabilized Phosphenium Oxides and Sulfides. Chemistry - A European Journal, 2012, 18 (50), pp.16153-16160. ⟨10.1002/chem.201202279⟩. ⟨hal-03731847⟩