Silicon hydride addition

Silane coupling agents are generally synthesized through addition of silicon hydrides to unsaturated organic molecules ... 

Newer silicone adhesives having solids levels up to 97% are also commercially available [109]. Instead of using silanol condensation reactions, they rely on addition chemistry between vinyl functional silicone oligomers and silicon hydride terminated silicones. This addition reaction is typically facilitated with platinum derived catalysts. This hydrosilation process can be run at reduced oven temperatures, but the finished products typically do not yield the same balance of properties as seen for condensation cure materials. 

Although there are several possible methods for the synthesis of organofunctionally terminated disiloxanes, hydrosilation reactions have become the most popular and practical process. Hydrosilation is the term used for the addition of silicon hydrides... 

Silicones can be prepared in such a way that they contain only one percent or less of vinyl groups and silicon hydrides, which undergo a catalytic hydrosilylation reaction to give the desired cross-linking (Figure 18.3). Vinyl silanes are made by Si-H addition to acetylene, and thus two hydrosilylations are involved. 

The kinetic data for halogenated carbon-centred radicals with silicon hydrides are also numerous and a few examples are shown in Table 3.2. The kinetic data for perfluoroalkyl radicals were obtained by competition of the appropriate silane with the addition to an olefin [16-18]. The kinetic deuterium isotope effects (/ h/ d) on the attack of on the Si—D bond of... 

The addition reaction of alkyl and/or phenyl substituted silicon hydrides to acetylenes has limitations mainly due to the hydrogen donation step (cf. Scheme 5.1). Reaction (5.17) shows that the replacement of Ph by MesSi group in silanes made the reaction easier, the effect being cumulative. Indeed, the reaction time decreased from 88 h for PhsSiH to 3h for (TMS)3SiH [39], together with the amelioration of yields, and a slightly better cis stereoselectivity. 

The reduction of ketones with silicon hydrides has been occasionally performed by radical chemistry for a synthetic purpose. The radical adduct is stabilized by the a-silyloxyl substituent and for RsSi (R = alkyl and/or phenyl) the hydrogen abstraction from the parent silane is much slower than a primary alkyl radical (cf. Chapter 3). On the other hand, (TMS)3SiH undergoes synthetically useful addition to the carbonyl group and the reactions with dialkyl ketones afford yields > 70% under standard experimental conditions, i.e., AIBN, 80-85 °C [45,51]. Reaction (5.25) shows as an example the reduction of 4-tcrt-butyl-... 

Scheme 7.6 Oxidative addition of silicon hydride to surface rhodium(diene) siloxide complex 1.

In this paper detailed methods for the determination of placement and assay of silicon hydride (Si-H), silicon hydroxide (Si-OH) and silicon phenyl (Si-0) functional groups in molecular weight components of silicones of the Sylgard (Dow-Corning Co.) type will be described. The methods are illustrated with the analysis of Sylgard addition prepolymers and of model polydimethylsiloxanes (PDMS). 

John Harrod and I have been looking at the silicon hydride addition to olefins catalyzed by Pt(II)... 

The formulation ofmoisture-ujriiig silicones includes a silicone polymer, filler, a moisture-reactive cross-linker, and sometimes a catalyst. A newer class of silicone sealants are known as the silicone latex sealants. These sealants are silicone-in-water emulsions that cure by evaporation of the emulsifying water. Addition-curing silicones in general are two-part systems that cure by the platinum-catalyzed reaction of a silicone hydride with typically a vinyl group attached to silicon. Because no by-products are generated by the cure, there are few volatiles and no shrink in thick sections. 

Germanium and silicon hydrides should be even more selective toward alkoxyl radicals relative to carbon radicals. Indeed, while silicon hydrides react rapidly with alkoxyl radicals, reactions with carbon radicals are too slow to propagate chains. The rapid addition of silyl and germyl radicals to C—O bonds is a possible complicating reaction. 

Hydrosilylation is by far the most important route for obtaining monomers and other precursors to fluorinated polysiloxanes. Hydrosylilation80 is the addition of silicon hydride moiety across an unsaturated linkage using transition metal complexes of platinum or rhodium such as Speier s catalyst, hexachloroplatinic acid in isopro-... 

Thicker sections can be cross-linked by hydrosilylation addition. This is the same chemistry used to produce fluorosilicone monomers with the vinyl functionality present on silicon. The catalyst reaction occurs between a vinyl group and silicone hydride.66 The advantage of this system is that it does not produce volatile by-products. On the other hand, the disadvantage is that it is available only as a two-part system.67 Recently, however, one-part, platinum-catalyzed products have been developed.66 The reaction is very rapid and at room temperature it is completed in 10 to 30 minutes. It is accelerated with increasing temperature and at 150°C (302°F) it is completed within a few seconds. This makes the compounds ideal for fast automated injection molding operations.68 One-part systems use the chemical complexing of the catalyst, which is activated at elevated temperatures, or its encapsulation into an impermeable shell, which is solid at room temperature and melts at elevated temperatures68... 

Graham137,141 Reactions of the type shown in Eqs. (12) and (13) pertain to oxidative eliminations or oxidative addition-elimination reactions. Further examples in which the transition metals increase their oxidation number by two and their coordination number by one are seen in the interaction of rho-dium(I)61 126, 127 186 iridium(I)1 2 123 and ruthenium(O) complexes160 with silicon hydrides ... 

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