Gas-phase solvolysis type reactions of SiCl3+ cations

Química Nova

Thiago Diamond Reis Firmino¹  Jair J. Menegon¹  José M. Riveros¹ 

[1] ,Universidade de São Paulo Instituto de Química São Paulo SP

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

DOI  :  10.1590/S0100-40422010001000018

来源: SciELO

【 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】

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