Artículos de revistas
Gas-phase solvolysis type reactions of SiCl3+ cations
Fecha
2010Registro en:
Química Nova, v.33, n.10, p.2098-2102, 2010
0100-4042
10.1590/S0100-40422010001000018
Autor
FIRMINO, Thiago Diamond Reis
MENEGON, Jair J.
RIVEROS, José M.
Institución
Resumen
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.