99798-82-0Relevant articles and documents
Iridium Pincer Catalysts for Silane Dehydrocoupling: Ligand Effects on Selectivity and Activity
Mucha, Neil T.,Waterman, Rory
supporting information, p. 3865 - 3872 (2015/08/19)
Catalytic reactions of bisphosphinite pincer-ligated iridium compounds p-XR(POCOP)IrHCl (POCOP) [2,6-(R2PO)2C6H3, R = iPr, X = H (1); R = tBu, X = COOMe (2); = H (3); = NMe2 (4)] with primary and secondary silanes have been performed. Complex 1 is primarily a silane redistribution precatalyst, but dehydrocoupling catalysis is observed for sterically demanding silane substrates or with aggressive removal of H2. The bulkier compounds (2-4) are silane dehydrocoupling precatalysts that also undergo competitive redistribution with less hindered substrates. Products generated from reactions utilizing 2-4 include low molecular weight oligosilanes with varying degrees of redistribution present or disilanes when employing more sterically demanding silane substrates. Selectivity for redistribution versus dehydrocoupling depends on the steric and electronic environment of the metal but can also be affected by reaction conditions. (Chemical Equation Presented).
Efficient synthesis of substituted diarylsilanes
Gigler, Peter,Herrmann, Wolfgang A.,Kuehn, Fritz E.
experimental part, p. 1431 - 1432 (2010/09/14)
A highly efficient synthesis of substituted diarylsilanes is presented. The treatment of substituted arylbromides with tert-bu-tyllithium in diethyl ether at -78 °C, followed by the addition to dichlorodiethoxysilane at the same temperature, leads to the quantitative formation of diaryldiethoxysilane. Selective substitution of the chlorine atoms allows an aqueous work up in air. Subsequently, the diaryldiethoxysilane is reduced to the corresponding diarylsi-lane by stirring with lithium aluminum hydride in diethyl ether. The product is purified by bulb-to-bulb distillation. This method does not lead to any mono- or tri-substituted products and avoids handling gaseous and explosive dichlorosilane, which is a significant advantage over previously reported procedures. Georg Thieme Verlag Stuttgart.
Base-catalyzed dehydrogenative Si-o coupling of dihydrosilanes: Silylene protection of diols
Grajewska, Agnieszka,Oestreich, Martin
supporting information; experimental part, p. 2482 - 2484 (2010/11/18)
The direct dehydrogenative coupling of 1,3- and 1,4-diols and dihydrosilanes is efficiently catalyzed by CsO(10 mol%), cleanly affording six- and seven-membered 1,3-dioxo-2-silacycles with dihydrogen as the sole by-product. Conversely, 1,2-diols do not yield the expected 1,3-dioxo-2- silacyclopentanes, essentially forming cyclic disiloxanes instead. Aside from the synthetic convenience, the procedure itself is also useful for straight-forward diol derivatization prior to GLC analysis. Georg Thieme Verlag Stuttgart · New York.
