title: Kinetic Control in the Cleavage of Unsymmetrical Disilanes.
abstract: A series of 12 phenyl-substituted arylpentamethyldisilanes 1a-l have been synthesized in order to examine the regioselectivity of their nucleophilic Si,Si bond cleavage reactions under Still's conditions (MeLi/HMPA/0 degrees C). It has been found that the sensitivity of these reactions to the electronic effects of the substituents in the phenyl ring could be described by the Hammett-type equation log(k(A)/k(B)) = 0.4334 + 2.421(Sigmasigma); (correlation coefficient R = 0.983). The k(A)/k(B) ratio represents the relative rate of attack at silicon atom A (linked to the aryl ring) or at silicon atom B (away from the aryl ring) of the unsymmetrical disilanes. Thus, the present investigation shows that the earlier belief according to which the nucleophilic cleavage of unsymmetrical disilanes always produces the more stable silyl anionic species (thermodynamic control) should be abandoned, or at least seriously amended: kinetic factors appear to exert a primary influence on the regioselectivity of such reactions. Since the two major kinetic factors (i.e., electrophilic character of and steric hindrance at a given silicon atom) have opposite effects on the orientation of the reaction, it may happen that kinetic and thermodynamic control lead to the same result. For some of the unsymmetrical disilanes studied, the major reaction path was not the Si,Si bond cleavage; instead, Si-aryl bond breaking occurred, producing the corresponding aryl anions.
authors.affiliation: Department of Chemistry, Facultés Universitaires Notre-Dame de la Paix, 61, rue de Bruxelles, B-5000 Namur, Belgium.
authors.forename: Làszlò
authors.initials: L
authors.lastname: Hevesi
authors.forename: Michael
authors.initials: M
authors.lastname: Dehon
authors.forename: Raphael
authors.initials: R
authors.lastname: Crutzen
authors.forename: Adriana
authors.initials: A
authors.lastname: Lazarescu-Grigore