Stable carbonium ions. LXXXV. Laser Raman and infrared spectroscopic study of alkylcarbonium ions

Abstract

was taken up in 2 ml of freshly distilled -pyrone (110°, 26 mm). 51 The flask was protected from the atmosphere (Drierite-KOH) and pyrolyzed for 75 min in an oil bath maintained at 145°. Aliquots were removed periodically, acidified, and subjected to analysis on a 6 ft X '/4 in. column of 10% DECS on Chromosorb W. No indene was observed.(B) The above procedure was repeated and aliquots of the gases from the reaction vessel were removed periodically during a 20min period and analyzed (Porapak Q) indicating a nitrogen-carbon dioxide ratio of 1:120.In the Presence of 1,2-Diazine. To 28 mg (0.21 mmol) of 9 and 160 mg (0.43 mmol) of 18-crown-6 ether in 2 ml of dry benzene was added 35 mg (0.88 mmol) of potassium hydride. The addition was carried out under nitrogen. After the bubbling ceased, the (51) . E.

Carbocations in Superacid Systems

“…Infrared and Raman spectra of stable carbocations have been obtained 71,72 and are in complete agreement with their electron-deficient structures. Infrared spectra of alkyl cations and their deuteriated analogs correspond to the spectra predicted by calculations based on molecular models and force constants.…”

Structures and Energetics of the tert‐Butyl Cation: The Final Answer or a Never‐Ending Story?

“…[2][3][4][5][6][7][8][9][10][11] Of the possible structures of the tert-butyl cation, C 3v was first suggested in 1971 by Olah et al [3] based on Raman and infrared spectroscopic studies. In another very important study (1989), Yannoni et al [6] reported that the best fit for the central carbonmethyl carbon distance was between 1.46 and 1.47 , whereas the C-C + -C bond angle is 1208 according to nutation NMR spectroscopy.…”

Calculated 11 B– 13 C NMR chemical shift relationship in hypercoordinate methonium and boronium ions

“…Olah et al (1) in 1971 discussed the relationship between (CH 3 ) 3 C ϩ and B(CH 3 ) 3 based on infrared and Raman spectroscopy. These studies provided unambiguous evidence that the two species possessed analogous structures and bondings.…”