Cyano-stabilized triphenylphosphonium ylids.
Crystalline cyano-stabilized triphenylphosphonium ylids with keto or ester groups give rise to an extended electronic delocalization. In methyl 2-cyano-2-(trimethylphosphonio)ethenoate, Ph3P=C(CN)CO2CH3 or C22H18NO2P, (I), and 1-cyano-1-(trimethylphosphonio)prop-1-en-2-olate, Ph3P=C(CN)CO-CH3 or C22H18NOP, (II), the carbonyl groups are oriented toward the cationoid P atom. Bond lengths and angles, torsion angles and P...O contact distances are consistent with a dominant coplanar conformation where the molecular structures are the result of a balance between intra- and intermolecular interactions. The main interactions presented by cyano-ester (I) and cyano-keto (II) are intramolecular interactions between the carbonyl O and the P atoms. In addition, both compounds show other less important intramolecular interactions between the carbonyl O and phenyl H atoms, which could contribute to form a preferred conformation in the crystal structure.
Castañeda
Fernando
F
Departamento de Química Orgánica y Fisicoquímica, Facultad de Ciencias, Químicas y Farmacéuticas, Universidad de Chile, Casilla 233, Santiago, Chile. fcastane@ciq.uchile.cl
Bunton
Clifford A
CA
Baggio
Ricardo
R
Garland
María Teresa
MT
D018360:Crystallography, X-Ray; D003485:Cyanates / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D008968:Molecular Conformation; D009943:Organophosphorus Compounds / Q000737:chemistry*
C518431:1-cyano-1-(trimethylphosphonio)prop-1-en-2-olate; D003485:Cyanates; D009943:Organophosphorus Compounds; C518430:methyl 2-cyano-2-(trimethylphosphonio)ethenoate