Gas-phase solvolysis type reactions of SiCl3+ cations

Quimica nova

Menegon, Jair J.¹  Firmino, Thiago Diamond Reis¹  Riveros, José M.¹ 

[1] Universidade de São Paulo, São Paulo

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 spectrometerreveal that these reactions are facile at 10-8 Torr and give riseto substituted chlorosilyl cations. Ab initio and DFT calculations revealthat these reactions proceed by addition of the silyl cation to the oxygen ornitrogen lone pair followed by a 1,3-H migration in the transition state. Thesetransition states are calculated to lie below the energy of the reactants. Bycomparison, hydrolysis of gaseous CCl3+ is calculatedto involve a substantial positive energy barrier.

【 授权许可】

CC BY