- PROCESS FOR THE STEPWISE SYNTHESIS OF SILAHYDROCARBONS
-
The invention relates to a process for the stepwise synthesis of silahydrocarbons bearing up to four different organyl substituents at the silicon atom, wherein the process includes at least one step a) of producing a bifunctional hydridochlorosilane by a redistribution reaction, selective chlorination of hydridosilanes with an ether/HCI reagent, or by selective chlorination of hydridosilanes with SiCI4, at least one step b) of submitting a bifunctional hydridochloromonosilane to a hydrosilylation reaction, at least one step c) of hydrogenation of a chloromonosilane, and a step d) in which a silahydrocarbon compound is obtained in a hydrosilylation reaction.
- -
-
Page/Page column 73; 85
(2021/12/08)
-
- Merging Platinum-Catalyzed Alkene Hydrosilylation with SiH4 Surrogates: Salt-Free Preparation of Trihydrosilanes
-
The monosilane (SiH4) surrogate di(cyclohexa-2,5-dien-1-yl)silane is shown to be compatible with platinum-catalyzed hydrosilylation of α-olefins. The cyclohexa-2,5-dien-1-yl substituents in the monohydrosilylation adducts serve as protecting groups, and treatment with catalytic amounts of B(C6F5)3 liberates the Si-H bonds along with benzene. By this, trihydrosilanes become accessible in two steps without the formation of salt waste.
- Smirnov, Polina,Oestreich, Martin
-
supporting information
p. 2433 - 2434
(2016/08/16)
-
- Formal SiH4 chemistry using stable and easy-to-handle surrogates
-
Monosilane (SiH4) is far less well behaved than its carbon analogue methane (CH4). It is a colourless gas that is industrially relevant as a source of elemental silicon, but its pyrophoric and explosive nature makes its handling and use challenging. Consequently, synthetic applications of SiH4 in academic laboratories are extremely rare and methodologies based on SiH4 are underdeveloped. Safe and controlled alternatives to the substituent redistribution approaches of hydrosilanes are desirable and cyclohexa-2,5-dien-1-ylsilanes where the cyclohexa-1,4-diene units serve as placeholders for the hydrogen atoms have been identified as potent surrogates of SiH4. We disclose here that the commercially available Lewis acid tris(pentafluorophenyl)borane, B(C6F5)3, is able to promote the release of the Si-H bond catalytically while subsequently enabling the hydrosilylation of C-C multiple bonds in the same pot. The net reactions are transition-metal-free transfer hydrosilylations with SiH4 as a building block for the preparation of various hydrosilanes.
- Simonneau, Antoine,Oestreich, Martin
-
p. 816 - 822
(2015/10/05)
-
- Iridium Pincer Catalysts for Silane Dehydrocoupling: Ligand Effects on Selectivity and Activity
-
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).
- Mucha, Neil T.,Waterman, Rory
-
supporting information
p. 3865 - 3872
(2015/08/19)
-
- CARBON-SILICON BOND CLEAVAGE OF ORGANOTRIALKOXYSILANES AND ORGANOSILATRANES WITH m-CHLOROPERBENZOIC ACID AND N-BROMOSUCCINIMIDE. NEW ROUTE TO PHENOLS, PRIMARY ALCOHOLS AND BROMIDES
-
Alkyl- and aryltriethoxysilanes undergo oxidative carbon-silicon bond cleavage smoothly with m-chloroperbenzoic acid (MCPBA) to afford the corresponding alcohols.Silatranes similarly gave alcohols and bromides with MCPBA and N-bromosuccinimide, respectively.
- Hosomi, Akira,Iijima, Susumu,Sakurai, Hideki
-
p. 243 - 246
(2007/10/02)
-
