P. Longevialle et O. Lefevre, ION-NEUTRAL REORIENTATION AND UNIMOLECULAR LOSS OF ALKANES FROM ORGANIC IONS IN THE GAS-PHASE, Organic mass spectrometry, 28(10), 1993, pp. 1083-1086
The loss of alkanes from ionized aliphatic alkanes alcohols, ketones,
ethers or amines takes place by a 1,2-elimination involving a C-C bond
cleavage and th specific rearrangement of a hydrogen atom to the inci
pient radical. This reaction should normally occur within a limited di
stance between the reactant sites. This condition is accomplished with
most probability during a concerted (or quasi-concerted) mechanism, b
efore the completion of the C-C bond cleavage. The same reaction may a
lso occur, however, in ion-neutral complexes, i.e. by a non-concerted
mechanism, after the C-C bond cleavage is completed, provided that the
probability is large enough for ion-neutral complexes to adopt suitab
le reactant configurations. This depends essentially on the proportion
of possible reacting sites in the whole molecular ion.