Nucleogenic cations were formed by beta-decay of phenylsilane tritiated at ortho- and para-positions of the benzene ring as well as at the silyl group and the products of their reactions with methyl tert-butyl ether were analyzed by radiochromatography. We found that the o-silatolyl cation was isomerized into the silabenzyl cation while the p-silatolyl cation was not. Furthermore, the silabenzyl cation was not converted into other isomers. The potential energy surface of the C6H7Si+ system was constructed by B3LYP and MP2 methods using an aug-cc-pVDZ basis set. Theory predicts the low barrier for o-silatolyl-silabenzyl isomerization but high barriers for hydride shifts in the ring from para. to meta- to ortho-isomers. It seems that nascent nucleogenic ions have enough internal energy to overcome the ortho-to-benzyl barrier but not enough to cross over the hydride-shift barriers. Theory also confirms that the isomerization of the silabenzyl cation to the [C6H6 center dot SiH](+) complex takes place in one step with a 62 kcal mol(-1) barrier, whereas that to either the global minimum [C6H7 center dot Si](+) or the silatropylium ion involves multisteps with 69-80 kcal/mol barriers. In addition,,we find that the barrier of interconversion between the [C6H6 center dot SiH](+) complex and one of the low-lying [C6H7 center dot Si](+) complexes is only 29 kcal/mol.