Carbene−Pnictinidene Adducts

• Published in: Inorganic chemistry 1997-05, Vol.36 (10), p.2151-2158
• Main Authors: Arduengo, Anthony J., Calabrese, Joseph C., Cowley, Alan H., Dias, H. V. Rasika, Goerlich, Jens R., Marshall, William J., Riegel, Bernhard
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic970174q

The syntheses, characterizations, and X-ray crystallographic structure determinations are described for adducts of stable nucleophilic carbenes with pnictinidenes. The adducts between 1,3-dimesitylimidazol-2-ylidene and phenylphosphinidene, phenylarsinidene, (trifluoromethyl)phosphinidene, and (pentafluorophenyl)arsinidene are reported. These carbene−pnictinidene adducts are formed by the direct reaction of a stable nucleophilic carbene with the corresponding pnictinidene cyclic oligomers. The synthesis and structure of the adduct between 1,3-dimesitylimidazolin-2-ylidene and phenylphosphinidene from the reaction of 1,3-dimesitylimidazolin-2-ylidene with phenylphosphorus dichloride are also reported. These carbene−pnictinidene adducts possess strongly polarized pnictinidene−carbene bonds. The C−Pn−C angles are all typically small at 97−102°, and there is only a 4% shortening of the nominal PnC double bond compared to the Pn−C single bond to the second substituent on the pnictogen. The 31P NMR shifts of the phosphorus adducts suggest strongly shielded phosphorus centers in accord with the polarized structures.