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Reactivity of vinylamine radical cation with neutral olefins: An example of ‘ionic’ free‐radical chemistry in the gas phase
Author(s) -
Bouchoux Guy,
PenaudBerruyer Florence
Publication year - 1993
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210280321
Subject(s) - chemistry , thermochemistry , cycloaddition , hydrogen atom abstraction , ionic bonding , photochemistry , hydrogen atom , fourier transform ion cyclotron resonance , computational chemistry , olefin fiber , hydrogen , ion , organic chemistry , alkyl , catalysis , polymer
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).