18033-75-5Relevant articles and documents
Nametkin et al.
, (1977)
Radiochemical study of the gas phase reaction of nucleogenic diethylsilylium ions with methanol and butanol
Kochina,Vrazhnov,Ignatyev
, p. 258 - 261 (2007/10/03)
The gas phase ion-molecule reactions between alcohols (methanol and n-butanol) and nucleogenic diethylsilylium ions generated by the β-decay of the tritiated diethylsilane were studied by the radiochromatographic method. Among the labelled neutral product
Substituent effects on the reactivity of the silicon-carbon double bond. Resonance, inductive, and steric effects of substituents at silicon on the reactivity of simple 1-methylsilenes
Leigh, William J.,Boukherroub, Rabah,Kerst, Corinna
, p. 9504 - 9512 (2007/10/03)
The reactivities of a series of substituted 1-methylsilenes RMeSi=CH2 (R = H, methyl, ethyl, t-butyl, vinyl, ethynyl, phenyl, trimethylsilyl, and trimethylsilymethyl) in hydrocarbon solvents have been investigated by far- UV (193-nm) laser flash photolysis techniques, using the corresponding 1- methylsilacyclobutane derivatives as silene precursors. Each of these silacyclobutanes yields ethylene and the corresponding silene, which can be trapped as the alkoxysilane RSiMe2OR' cleanly upon 193- or 214-nm photolysis in solution in the presence of aliphatic alcohols. UV absorption spectra and absolute rate constants for reaction of the silenes with methanol, ethanol, and t-butyl alcohol have been determined in hexane solution at 23°C. The rate constants vary from a low 3 x 107 M-1 s-1 for reaction of 1- methyl-1-trimethylsilylsilene with t-BuOH to a high of 1 x 1010 M-1 s- 1 for reaction of 1-ethynyl-1-methylsilene with MeOH. In several cases, rate constants have been determined for addition of the deuterated alcohols, and for addition of methanol over the 0-55°C range. Invariably, small primary deuterium kinetic isotope effects and negative Arrhenius activation energies are observed. These characteristics are consistent with a mechanism involving reversible formation of a silene-alcohol complex which collapses to alkoxysilane by unimolecular proton transfer from oxygen to carbon. Silene reactivity increases with increasing resonance electron-donating and inductive electron-withdrawing ability of the substituents at silicon and is significantly affected by steric effects within this series of compounds. This is suggested to be due to a combination of effects on both the degree of electrophilicity at silicon (affecting the rate constants for formation and reversion of the complex) and nucleophilicity at carbon (affecting the partitioning of the complex between product and free reactants). Two 1- methyl-1-alkoxysilacyclobutanes were also investigated, but proved to be inert to 193-nm photolysis.
