1997/05/01 by Anthony J. Arduengo, Joseph C. Calabrese, Alan H. Cowley +4 · 1 citation
Chemistry · #N-Heterocyclic Carbenes in Organic and Inorganic Chemistry #Synthesis and characterization of novel inorganic/organometallic compounds #Synthetic Organic Chemistry Methods #Carbene #Chemistry #Adduct #Phosphinidene #Nucleophile #Trifluoromethyl #Ylide #Medicinal chemistry #Substituent #Pnictogen #Stereochemistry #Crystallography #Organic chemistry #Catalysis
paper · doi:10.1021/ic970174q
openalex publication_date 1997/05/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/22
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 degrees, 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 (31)P NMR shifts of the phosphorus adducts suggest strongly shielded phosphorus centers in accord with the polarized structures.