Silicon vs. carbon containing ions: 1,3-proton transfers within the (CH3)(X)Si(OR)(+OHR ') units - École polytechnique Accéder directement au contenu
Article Dans Une Revue International Journal of Mass Spectrometry Année : 2002

Silicon vs. carbon containing ions: 1,3-proton transfers within the (CH3)(X)Si(OR)(+OHR ') units

Résumé

In the cell of an FT-ICR spectrometer, (CH3)(X)C(OCR)(+OHR') and (CH3)(X)Si(OCR)+OHR' (R and R'=H, CH3 or C2H5; X=H or CH3) covalent ions were generated by reaction of the (CH3)(X)+Si-OCR' cations with water or alcohols. In the so-formed covalent ions, experiment shows that 1,3-H+ transfers from oxygen to oxygen are often easy in silicon containing ions while they are not observed in the corresponding ions containing only carbon. Calculations indicate that the energy required for a 1,3-H+ transfer from oxygen to oxygen is almost identical whether the transition state contains a silicon atom or not. The greater strength of the Si-O bond in cations, compared to that of the C-O bond or, in other words, the great electrophilic character of cations possessing a Si+, is the main factor explaining the difference in the behavior of the studied silicon containing ions and ions containing exclusively carbon.

Dates et versions

hal-00918101 , version 1 (13-12-2013)

Identifiants

Citer

D Leblanc, Hristo Nedev, Henri E. Audier. Silicon vs. carbon containing ions: 1,3-proton transfers within the (CH3)(X)Si(OR)(+OHR ') units. International Journal of Mass Spectrometry, 2002, 219 (3), pp.537-547. ⟨10.1016/S1387-3806(02)00707-8⟩. ⟨hal-00918101⟩
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