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 G.; 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.

DOI: https://doi.org/10.1016/S0022-328X(03)00622-3

Abstract

Successful ring-expanding insertion reactions of T-6 silsesquioxane cages using dialkyl and diarylethoxysilanes have been performed to give the first reported mixed T6D1 and T6D2 silsesquioxane cages. The reactions of hexacyclohexylsilsesquioxane (T-6) with dialkyl and diaryldiethoxysilanes give predominantly T6D2 bis-insertion compounds while the reaction of T-6 with dimethylethoxysilane gives one T6D1 mono-insertion product and various T6D2 bis-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. (C) 2003 Elsevier B.V. All rights reserved.

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