REARRANGEMENTS IN METASTABLE ION DECOMPOSITIONS OF PROTONATED PROPYLAMINES

被引：41

作者：

AUDIER, HE ^{[1
]}

MORTON, TH ^{[1
]}

机构：

[1] UNIV CALIF RIVERSIDE, DEPT CHEM, RIVERSIDE, CA 92521 USA

来源：

ORGANIC MASS SPECTROMETRY | 1993年 / 28卷 / 10期

关键词：

D O I：

10.1002/oms.1210281037

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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, [iPr+ NH3], or rearrangement to iPrNH3+ is required. SCF calculations were used to probe the potential energy surface. There is a minimum corresponding to [iPr+ NH3], in which the nitrogen lone pair points towards the machine hydrogen and is 2.1 angstrom away from it, and another, less stable. minimum corresponding to a hydrogen-bonded structure, H3N...H3CCHCH3+, in which one methyl hydrogen is 2.0 angstrom 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.

引用

页码：1218 / 1224

页数：7