The reactions of dialkyl and diarylethoxysilanes with T₆ silsesquioxane cages X-ray crystallographic studies of the mono-T₆D₁ and bis-T₆D₂ insertion ring expansion products

Bassindale, Alan R.; Liu, Zhihua; Parker, David J.; Taylor, Peter; Horton, Peter N.; Hursthouse, Michael B. and Light, Mark E. (2003). The reactions of dialkyl and diarylethoxysilanes with T₆ silsesquioxane cages X-ray crystallographic studies of the mono-T₆D₁ and bis-T₆D₂ insertion ring expansion products. Journal of Organometallic Chemistry, 687(1) pp. 1–11.

URL: http://dx.doi.org/10.1016/S0022-328X(03)00622-3

Abstract

Successful ring-expanding insertion reactions of T₆ silsesquioxane cages using dialkyl and diarylethoxysilanes have been performed to give the first reported mixed T₆D₁ and T₆D₂ silsesquioxane cages. The reactions of hexacyclohexylsilsesquioxane (T₆) with dialkyl and diaryldiethoxysilanes give predominantly T₆D₂ bis-insertion compounds while the reaction of T₆ with dimethylethoxysilane gives one T₆D₁mono-insertion product and various T₆D₂bis-insertion products as isolable components. Three of the ring-expanded products are chiral and it has been shown from their X-ray crystal structures that the pairs of enantiomers, formed as racemic mixtures, co-crystallise together. As well as comparing these structures with related ones in the literature, the possible mechanism of their formation is discussed.

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