DISSOCIATIVE ATTACHMENT OF PROTONS TO 1-FLUOROADAMANTANE AND 1-CHLOROADAMANTANE IN THE GAS-PHASE

被引:41
作者
ABBOUD, JLM
NOTARIO, R
BALLESTEROS, E
HERREROS, M
MO, O
YANEZ, M
ELGUERO, J
BOYER, G
CLARAMUNT, R
机构
[1] CSIC, INST QUIM MED, E-28006 MADRID, SPAIN
[2] CIUDAD UNIV MADRID, UNED, DEPT QUIM ORGAN, E-28040 MADRID, SPAIN
[3] UNIV AUTONOMA MADRID, DEPT QUIM, E-28049 MADRID, SPAIN
关键词
D O I
10.1021/ja00085a032
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
An FTICR mass spectrometry study has shown that gas-phase protonation of 1-fluoro- and 1-chloroadamantane is followed by a carbon-halogen bond fission. This technique has also allowed the determination of the onset of these dissociative proton attachment reactions. The experimental findings are ratified by ab initio MO calculations showing that the equilibrium conformation of both protonated species correspond to an ion-dipole complex between the adamantyl cation and the corresponding hydrogen halide molecule. Both the theoretical and the experimental approaches indicate 1-fluoroadamantane to be more basic in the gas phase than 1-chloroadamantane. The structures and harmonic vibrational frequencies of the relevant species in these reactions are also examined.
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收藏
页码:2486 / 2492
页数:7
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