Radiochemical study of the reaction between the diethylsilylium cation andbenzene in gas and liquid phases: experimental and theoretical evidence for rearrangements of the diethylsilylium cation

The ion-molecule reaction between the nucleogenic diethylsilylium cation ge nerated by the beta-decay of the tritiated diethylsilane and benzene was st udied by the radiochromatographic method in the gas and liquid phases. Diet hylphenylsilane possessing the diethylsilyl group of the nascent cation has the lowest yield in the gas phase, although in the liquid phase the yield increases. Two other siIylphenylsilanes are products of rearrangement of th e diethylsilylium cation. The stationary points on the potential energy sur face of the SiC4H11+ system were located by the ab initio correlated method s and the plausible rearrangements within this system are discussed. (C) 19 99 Elsevier Science SA. All rights reserved.