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Carbene‐Stabilized Phosphenium Oxides and Sulfides
Author(s) -
Maaliki Carine,
Lepetit Christine,
Duhayon Carine,
Canac Yves,
Chauvin Remi
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201202279
Subject(s) - carbene , heterolysis , adduct , chemistry , nucleophile , homolysis , ligand (biochemistry) , dissociation (chemistry) , medicinal chemistry , crystallography , photochemistry , organic chemistry , catalysis , radical , biochemistry , receptor
Carbene→chalcogenophosphenium adducts, which correspond to an intermolecular stabilization mode of the so far elusive, free oxo‐ and thiooxophosphenium species [R 2 P + = X] (X=O, S) by imidazolylidene (NHC) and diaminocyclopropenylidene (BAC) donors, have been isolated and fully characterized. The dative character of the R 2 C:→P + (X)Ph 2 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)Ph 2 adduct with an independently prepared BAC ligand, thereby giving the BAC:→P + (O)Ph 2 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.