Experimental and ab initio MO studies on the IR spectra and structure of pyridinium dicyanomethylide and trimethylammonium dicyanomethylide.
The structures of the title ylides have been studied by both quantitative infrared (IR) spectra and ab initio HF and MP2 force field calculations. Good agreement has been found between theoretical and experimental data for their spectral and structural characteristics. According to both IR data and geometry parameters the dicyanomethide groups in the ylides studied have a pronounced carbanionic character. The analysis of the calculated net electric charges however shows only moderate (below 0.6 e-) intramolecular charge transfers between the pyridinium (trimethylammonium) and dicyanomethide fragments of the species studied.
Binev
Y I
YI
Institute of Organic Chemistry, Bulgarian Academy of Sciences, Sofia.
Stamboliyska
B A
BA
Binev
I G
IG
D008958:Models, Molecular; D008962:Models, Theoretical; D008968:Molecular Conformation; D009570:Nitriles / Q000737:chemistry*; D011726:Pyridinium Compounds / Q000737:chemistry*; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D013055:Spectrophotometry, Infrared / Q000379:methods; D013329:Structure-Activity Relationship
D009570:Nitriles; D011726:Pyridinium Compounds; D000644:Quaternary Ammonium Compounds; C425154:pyridinium dicyanomethylide; C425155:trimethylammonium dicyanomethylide