The pulsed laser photolysis-resonance fluorescence technique has been used to determine the absolute rate coefficient for the Cl atom reaction with a series of ketones, at room temperature (298 ฯฎ 2) K and in the pressure range 15-60 Torr. The rate coefficients obtained (in units of cm 3 molecule ฯช1
Reactions of silyl cations with ketones in the gas phase
โ Scribed by Leblanc, D.; Audier, H. E.; Denhez, J. P.
- Publisher
- John Wiley and Sons
- Year
- 1999
- Tongue
- English
- Weight
- 85 KB
- Volume
- 34
- Category
- Article
- ISSN
- 1076-5174
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โฆ Synopsis
In the gas phase, (CH 3 ) 3 SiOSi Y (CH 3 ) 2 and (CH 3 )CH 2 SiOSi Y (CH 3 ) 2 ions 1 and 2 were formed in the external source of a Fourier transform ion cyclofrom resonance (FT-ICR) spectrometer by electron impact ionization of (CH 3 ) 3 SiOSi(CH 3 ) 3 . In the FT-ICR cell, the electrophilic center of these ions reacts with acetone to give product ions whose structures are probed by comparison with those of the products formed by reaction with water. The mechanisms of formation of these products, studied by labeling, involve facile 1,3-methyl transfer from silicon to silicon and cyclic intermediates.
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