Speier reaction

Both HSiCl3 and HGeCl3 will add across double bonds in a process known as the Speier reaction. This reaction can be shown as follows ... 

An important reaction of HSiCl3 and HGeCl3 is their addition across double bonds in alkenes. This reaction is known as the Speier reaction, and it leads to alkyl trichloro derivatives ... 

Attempted HaPtClj-catalysed (Speier reaction) addition of Me,SiH or MeSiHOj to [(CF3)aN]gC CHa failed (even at 160 °C for 72 h) the yields of the ethenyl-silanes in the photochemical reactions were high but conversions were low (X = Me, 95% yield, 35% conv. of olefin X = Cl, 93, 40%), and the following mechanism was postulated ... 

The most common catalyst used to date is chloroplatinic acid (also known, after its discoverer, as Speier s catalyst) it is now clear that, contrary to earlier views (23), hydrosilylation is a homogeneous process (25, 208). A major problem is that of reproducibility, and efforts are being made to utilize soluble transition metal complexes. Information about such systems has been used in the interpretation of some related catalytic heterogeneous reactions (232). 

The hydrosi(ly)lations of alkenes and alkynes are very important catalytic processes for the synthesis of alkyl- and alkenyl-silanes, respectively, which can be further transformed into aldehydes, ketones or alcohols by estabhshed stoichiometric organic transformations, or used as nucleophiles in cross-coupling reactions. Hydrosilylation is also used for the derivatisation of Si containing polymers. The drawbacks of the most widespread hydrosilylation catalysts [the Speier s system, H PtCl/PrOH, and Karstedt s complex [Pt2(divinyl-disiloxane)3] include the formation of side-products, in addition to the desired anh-Markovnikov Si-H addition product. In the hydrosilylation of alkynes, formation of di-silanes (by competing further reaction of the product alkenyl-silane) and of geometrical isomers (a-isomer from the Markovnikov addition and Z-p and -P from the anh-Markovnikov addition. Scheme 2.6) are also possible. 

The hydrosilylation of alkynes has also been studied using as catalysts Pt, Rh, Ir and Ni complexes. The improvement of the regioselectivity of the catalyst and the understanding of stereoelectronic factors that control it have been major incentives for the ongoing research. From numerous studies involving non-NHC catalysts, it has been established that there is a complex dependence of the product ratio on the type of metal, the aUcyne, the metal coordination sphere, the charge (cationic versus neutral) of the catalytic complex and the reaction conditions. In the Speier s and Karstedt s systems, mixtures of the thermodynamically more stable a- and -E-isomers are observed. Bulky phosphine ligands have been used on many occasions in order to obtain selectively P-f -isomers. 

Under the same reaction conditions traditional catalysts, such as H2PtCl6 in PrOH (Speier catalyst) and Pt2(divinyltetramethyldisiloxane)3 (Karstedt Catalyst) are completely inactive. 

The ubiquitous hydrosilation reaction, popular especially in silicone manufacturing,132 has been utilized by Houser and Keller for the synthesis of the networked polymers (104) (Fig. 64) from the reaction of the l,7-bis(vinyltetramethyldisiloxyl)-w-carborane monomer with the polymeric crosslinker, poly(methylhydrosiloxane).133 The reactions were catalyzed by the Speier s catalyst, H2PtCl6. Three samples were... 

Transition-metal chemistry is currently one of the most rapidly developing research areas. The record of investigation for compounds with metal silicon bonds is closely comparable to that for silicones it was in 1941 when Hein discovered the first metal silicon complex, followed by Wilkinson in 1956. A milestone in the development of this chemistry was Speier s discovery of the catalytic activity of nobel metal complexes in hydrosilylation reactions in 1977. Hydrosilylation is widely used in modem organic syntheses as well as in the preparation of organo functionalized silicones. Detailed investigations of the reaction mechanisms of various catalysts continue to be subject of intense research efforts. 

The autoxidation of 3,5-di-terf-butylcatechol (H2DTBC) was frequently used to test the catalytic activity of various metal complexes. Speier studied the reaction with [Cu(PY)Cl] (PY = pyridine) in CH2C12 and CHCI3, and reported second-, first- and zeroth-order dependence with respect to Cu(I), 02 and substrate concentrations, respectively (41). The results are consistent with a kinetic model in which the rate determining oxidation of Cu(I) is followed by fast reduction of Cu(II) by H2DTBC. 

We have studied polyhydrosilylation reactions of a/o-oligodiorganodihydnde siloxanes and l,4-bis(dihydridedimetylsilyl)benzene with dialylsilazanes (DAS) in the presence of Speier s catalyst (0.1 mole solution of H2PtCl6 6H20 in isopropanol) [3-7] in dry toluene and in mass. 

The CVD method can form a polymethylsiloxane layer of 0.6-0.8 nm on the inorganic particles (Table 12.1.2). Especially, the polysiloxane-modified titanium oxide has been used for the additives to cosmetics. Moreover, residual Si-H group grafted on the particles reacted with unsaturated organic compounds in the presence of Speier catalyst (47), H2PtCl6, to be functionalized by organic pendant group [Reaction (11 ). ... 

Hydrosilylation of divinyl ether has been applied for the synthesis of silacyclopentane 12 using Speier s catalyst (Scheme l)13. One of the two carbon-carbon double bonds was hydrosilylated first with a dialkyl(ethoxy)silane, giving silylethyl vinyl ether 10 in 53-59% yield, which was reduced with LiAlELr to hydrosilane 11. The intramolecular hydrosilylation of 11 affords silacyclopentane 12 in moderate yields (Scheme 1). The reaction with HSiEt2(OEt) gives 12a exclusively in 45% yield, while silacyclohexane 13b is formed as the minor product when HSiMe2(OEt) is used as the hydrosilane (12b/13b = 2.3/1 50% total yield)13. Other intramolecular hydrosilylation reactions useful in organic syntheses will be discussed in the section n.C. (vide infra). 

Saran M, Beck-Speier I, Fellerhoff B, Bauer G (1999) Phagocytic killing of microorganisms by radical processes consequences of the reaction of hydroxyl radicals with chloride yielding chlorine atoms. Free Rad Biol Med 26 482-490... 

This reaction is catalyzed by a platinum catalyst such as Speier s catalyst, chloroplatinic acid. Because the catalyst also isomerizes the terminal double bond, the reaction maybe run with an excess of vinyl to make sure all the reactive sites on the silicone are reacted. SiH also reacts with ROH and, for this reason, alkoxy end-capped polyethers maybe preferred. Alkoxy end-capped polyethers are also useful when the surfactant will be used in a chemically reactive system such as polyurethane foam manufacture. 

Perhaps the most important reaction of compounds with an Si—H bond, such as Cl3SiH or Me3SiH, and one that is of commercial importance, is the Speier or hydrosilation29 reaction of alkenes, for example ... 

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