Gas-phase solvolysis type reactions of SiCl3+ cations

Química Nova

Menegon, Jair J.¹  Universidade Federal do ABC, Santo André, Brasil¹  Firmino, Thiago Diamond Reis¹  Riveros, José M.¹  Universidade de São Paulo, São Paulo¹ 

关键词: silicylium ions;    gas-phase;    solvolyses.;   

DOI  :  10.1590/S0100-40422010001000018

学科分类：化学（综合）

来源: Sociedade Brasileira de Quimica

【 摘 要 】

Gas-phase SiCl3+ ions undergo sequential solvolysis type reactions with water, methanol, ammonia, methylamine and propylene. Studies carried out in a Fourier Transform mass spectrometer reveal that these reactions are facile at 10-8 Torr and give rise to substituted chlorosilyl cations. Ab initio and DFT calculations reveal that these reactions proceed by addition of the silyl cation to the oxygen or nitrogen lone pair followed by a 1,3-H migration in the transition state. These transition states are calculated to lie below the energy of the reactants. By comparison, hydrolysis of gaseous CCl3+ is calculated to involve a substantial positive energy barrier.

【 授权许可】

Unknown