Reactivity of vinylamine radical cation with neutral olefins: An example of ‘ionic’ free-radical chemistry in the gas phase

✍ Scribed by Guy Bouchoux; Florence Penaud-Berruyer

• Publisher: John Wiley and Sons
• Year: 1993
• Tongue: English
• Weight: 667 KB
• Volume: 28
• Category: Article
• ISSN: 1076-5174
• DOI: 10.1002/oms.1210280321

✦ Synopsis

Hydrogen atom abstraction and cycloaddition-cycloreversion reactions between ionized vinylamine and neutral olefins were studied in a Fourier transform ion cyclotron resonance spectrometer. The efficiencies of both processes are appreciably less than unity. The trend in reaction efficiencies is consistent with the presence of a substantial intrinsic barrier but interpretation based on constraints inherent to the approach of the reactants cannot be discarded. The regioselectivity observed during the cycloaddition-cycloreversion reactions closely parallels the nucleophilic attack of an olefin by a free radical. The thermochemistry of these reactions and partial potential energy surfaces were examined with the help of experimental data and molecular orbital calculations (MP2/6-31G*//3- 21G).