Quimica nova | |
Gas-phase solvolysis type reactions of SiCl3+ cations | |
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
【 预 览 】
Files | Size | Format | View |
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RO201902011870186ZK.pdf | 801KB | download |