Reducing agents silane reactions

Lithium hydride is perhaps the most usehil of the other metal hydrides. The principal limitation is poor solubiUty, which essentially limits reaction media to such solvents as dioxane and dibutyl ether. Sodium hydride, which is too insoluble to function efficiently in solvents, is an effective reducing agent for the production of silane when dissolved in a LiCl—KCl eutectic at 348°C (63—65). Magnesium hydride has also been shown to be effective in the reduction of chloro- and fluorosilanes in solvent systems (66) and eutectic melts (67). 

The reaction of carbon-centered radicals with silicon hydrides is of great importance in chemical transformations under reducing conditions where an appropriate silane is either the reducing agent or the mediator for the formation of new bonds.23... 

Although under canonical radical chain conditions these silanes are poor reducing agents, there are some interesting applications, in particular, using Ph2SiH2 [100]. For example, the reaction of a variety of substituted adamantanes... 

The different types of admixtures, known to reduce alkali-aggregate reactions, can be divided into two groups those that are effective in reducing the expansion due to the alkali-silica reaction, and those that lower expansions resulting from the alkali-carbonate reaction. For the alkali-silica reaction, reductions in the expansion of mortar specimens have been obtained with soluble salts of lithium, barium and sodium, proteinaceous air-entraining agents, aluminum powder, CUSO4, sodium silicofluoride, alkyl alkoxy silane,... 

Tris(trimethylsilyl)silane is found to be an efficient reducing agent for a variety of functional groups. In particular, the reduction of halides, chalcogen groups, thiono esters and isocyanides are the most common ones. The efficiency of these reactions is also supported by available kinetic data. The rate constants for the reaction of (TMS)3Si radicals with a variety of organic substrates are collected in Table 2. 

Polystyrene-bound silanes are usually prepared by reaction of organolithium compounds with resin-bound silyl chlorides [12, 13]. The C-Si bonds of aryl-, heteroaryl-, vinyl-, and allylsilanes are stable towards alcoholates or weak reducing agents, but can be cleaved under mild conditions by treatment with acids or fluoride to yield a hydrocarbon and a silyl ester or silyl fluoride. Several linkers of this type have been tested and have proven useful for the preparation of unfunctionalized arenes and alkenes upon cleavage from insoluble supports. 

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