REACTIONS OF HYDROSILSESQUIOXANES AND CHLOROSILSESQUIOXANES WITH PHOSPHORANES

Monofunctional hydro- and chloro-silsesquioxanes react with phoshorane s to give high yields of phosphorane-substituted frameworks. The react ion of [(c-C6H11)(7)Si8O12(H)] (1a) with Me(3)PCH(2) (2 equiv) produce s Me(3)P, methane, and high yields of [(c-C6H11)(7)Si8O12(CHPMe(3))] ( 2a), which can also be obtained from the reaction of Me(3)PCH(2) (2 eq uiv) with [(c-C6H11)(7)Si8O12(Cl)] (1c). Mechanisms are suggested for both transformations. Hydrosilsesquioxane 1a does not react with Ph(3) PCH(2), but 1c reacts with Ph(3)PCH(2) to afford high yields of [(c-C6 H11)(7)Si8O12(CHPPh(3))] (2b). Both 2a and 2b react as Wittig reagents with a variety of aldehydes to afford high yields of the correspondin g olefination products.