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Gas‐phase association reactions of trimethylsilylium ((CH 3 ) 3 Si + ) with organic bases
Author(s) -
Stone John A.
Publication year - 1997
Publication title -
mass spectrometry reviews
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.035
H-Index - 126
eISSN - 1098-2787
pISSN - 0277-7037
DOI - 10.1002/(sici)1098-2787(1997)16:1<25::aid-mas2>3.0.co;2-c
Subject(s) - chemistry , mass spectrometry , adduct , yield (engineering) , ionization , gas phase , halide , ion , intramolecular force , analytical chemistry (journal) , thermodynamics , organic chemistry , physics , chromatography
This article is a review of the gas‐phase association reactions of (CH 3 ) 3 Si + with organic bases. The reactions are considered under the headings of the three pressure regimes under which they are studied. ICR and FTICR studies, carried out at pressures of 10 −5 and lower, allow insights into the stabilizations, collisional and radiative, and decompositions of the nascent adducts. At pressures around 2 Torr, chemical ionization studies demonstrate the utility and limitations of (CH 3 ) 3 Si + as a reagent ion, whereas high‐pressure mass spectrometric and flowing afterglow experiments yield information on the thermodynamics of the association reactions. Information is also obtained on the stabilization of alkyl and vinyl cations by a (CH 3 ) 3 Si group in a position β to the charge site. High pressure (∼ 1 atmosphere) γ‐radiolytic experiments give detailed information of the neutral products formed via the association reactions and also yield relative rate data for inter‐ and intramolecular processes that occur in the energy‐rich adducts prior to collisional stabilization and neutralization. The ease of experimentation with R 3 Si + in the gas phase is contrasted with the difficulty of its recognition and observation in the condensed phase. © 1997 John Wiley & Sons, Inc., Mass Spectrom Rev 16(1), 25–49, 1997