Pescarmona Paolo P, van der Waal Jan C, Maschmeyer Thomas
Laboratory of Applied Organic Chemistry and Catalysis, DelftChemTech, Technische Universiteit Delft, Julianalaan 136, 2628 BL Delft, The Netherlands.
Chemistry. 2004 Apr 2;10(7):1657-65. doi: 10.1002/chem.200305387.
A set of new titanium-silsesquioxane epoxidation catalysts was discovered by exploring the hydrolytic condensation of a series of trichlorosilanes in highly polar solvents by means of high-speed experimentation techniques. The most promising silsesquioxane leads were prepared on a conventional laboratory scale and fully characterised. The lead generated by the hydrolytic condensation of tBuSiCl(3) in DMSO consisted of a set of incompletely condensed silsesquioxane structures, whereas that obtained from the hydrolytic condensation of tBuSiCl(3) in water consisted of a single silsesquioxane structure, tBu(2)Si(2)O(OH)(4). This is the first reported example of the use of this silsesquioxane as a precursor for active Ti catalysts. The Ti complexes prepared with tBu(2)Si(2)O(OH)(4) were supported on silica to produce active heterogeneous epoxidation catalysts.
通过高速实验技术探索一系列三氯硅烷在高极性溶剂中的水解缩合反应，发现了一组新型钛硅倍半氧烷环氧化催化剂。在常规实验室规模下制备了最具潜力的硅倍半氧烷先导化合物，并对其进行了全面表征。在二甲基亚砜中tBuSiCl(3)水解缩合生成的先导化合物由一组不完全缩合的硅倍半氧烷结构组成，而在水中tBuSiCl(3)水解缩合得到的先导化合物则由单一的硅倍半氧烷结构tBu(2)Si(2)O(OH)(4)组成。这是首次报道使用这种硅倍半氧烷作为活性钛催化剂前体的例子。用tBu(2)Si(2)O(OH)(4)制备的钛配合物负载在二氧化硅上，制得活性非均相环氧化催化剂。
