Rearrangements in Metastable Ion Decompositions of Protonated Propylamines

Article abstract of DOI:10.1002/oms.1210281037

Decomposition of nPrNH3(+) to NH4(+) does not occur via vicinal elimination.Hydrogen transfer takes place from all positions of the alkyl chain.Intermediacy of either an ion-neutral complex, , or rearrangement to iPrNH3(+) is required.SCF calculations were used to probe the potential energy surface.There is a minimum corresponding to , in which the nitrogen lone pair points towards the machine hydrogen and is 2.1 Angstroem away from it, and another, less stable, minimum corresponding to a hydrogen-bonded structure, H3N ...H3CCHCH3(+), in which one methyl hydrogen is 2.0 Angstroem from the nitrogen.Density of states estimates suggest that a vibrationally excited complex can live for the order of 100 ps before either collapsing to iPrNH3(+) or yielding NH4(+) and propene.