Abstract
AbstractThe hydrolysis of some p‐substituted triphenylsilanes in the presence of tetrabutyl‐ammonium hydroxide has been investigated in various water‐acetonitrile media with the aim of comparing the results with those already published for triphenylsilane. It appears that the initial rate is first order with respect to both silane and base whereas the order during the time is not constant for some silanes, depending on the water composition. The second order rate constant varies in agreement with the Hammett substituent constant σp. From the calculations of the transfer Gibbs functions for the activated state and for OH− from a reference medium (water mole fraction = 0.225), it is concluded that the solvent effect is not fundamentally altered by the p‐substituents and that the medium influence on the rate can be essentially attributed to solvation modifications around OH−.
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