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• W2058849017 abstract "The incompletely condensed monosilylated silsesquioxanes (c-C5H9)7Si7O9(OSiRR‘2)(OH)2 (SiRR‘2 = SiMe3, SiMe2C(H)CH2, SiMePh2) were reacted with SiCl4 in the presence of an amine which yielded the dichloro compounds (c-C5H9)7Si7O9(OSiRR‘2)O2SiCl2 (1−3). These compounds could be hydrolyzed into the corresponding silsesquioxanes containing geminal silanols, (c-C5H9)7Si7O9(OSiRR‘2)O2Si(OH)2 (4−6). At elevated temperatures, the geminal silsesquioxanes 4 and 5 undergo condensation reactions and form the closed-cage silsesquioxane monosilanol, (c-C5H9)7Si8O12(OH). The more sterically hindered geminal silsesquioxane 6 undergoes in solution intermolecular dehydroxylation, yielding the thermodynamically stable dimeric disilanol, [(c-C5H9)7Si7O9(OSiMePh2)(O2Si(OH)-)]2-(μ-O) (7). NMR and FT-IR studies show that the two silanols of the geminal silsesquioxanes 4−6 are different from each other with respect to hydrogen bonding, both in solution and in the solid state. Hydrogen bonding of the geminal silanol-containing silsesquioxanes was examined and compared to hydrogen bonding in silsesquioxanes possessing vicinal or isolated silanol groups. The relative Brønsted acidity of the geminal silanols was determined using pKip (ion-pair acidity) measurements in THF with UV−vis. These acidities were compared with those of other silsesquioxanes containing silanol groups. Acidities of 4−6 were found to be among the lowest known for silsesquioxanes." @default.
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• W2058849017 date "2002-07-30" @default.
• W2058849017 modified "2023-10-16" @default.
• W2058849017 title "Silsesquioxane Models for Geminal Silica Surface Silanol Sites. A Spectroscopic Investigation of Different Types of Silanols" @default.
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• W2058849017 doi "https://doi.org/10.1021/ja0122243" @default.
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