Silicon-hydrogen bonds

The oxidative addition of silanes (with silicon-hydrogen bonds) to coordinatively unsaturated metal complexes is one of the most elegant methods for the formation of metal-silicon bonds. Under this heading normally reactions are considered which yield stable silyl metal hydrides. However, in some cases the oxidative addition is accompanied by a subsequent reductive elimination of, e.g., hydrogen, and only the products of the elimination step can be isolated. Such reactions are considered in this section as well. 

Mixing trichlorosilane, acetonitrile and diphenylsulphoxide, carried out at 10°C, detonated. This accident was put down to the exothermic addition reaction of the silicon-hydrogen bond on the carbon-nitrogen triple bond of nitrile. Other interpretations are possible for instance, the effect of traces of hydrogen chloride formed by the hydrolysis of chlorosilane on acetonitrile. 

The hydrogen content Ch greatly influences structure and consequently electronic and optoelectronic properties. An accurate measurement of Ch can be made with several ion-beam-based methods see e.g. Arnold Bik et al. [54]. A much easier accessible method is Fourier-transform infrared transmittance (FTIR) spectroscopy. The absorption of IR radiation is different for different silicon-hydrogen bonding configurations. The observed absorption peaks have been indentified [55-57] (for an overview, see Luft and Tsuo [6]). The hydrogen content can be determined from the absorption peak at 630 cm , which includes... 

In order to distinguish between isolated silicon-hydrogen bonds in a dense network and other bonding configurations, such as clustered monohydride and dihydride bonds, bonds on internal void surfaces, and isolated dihydride bonds, Mahan et al. [60] have defined the microstructure factor R as... 

Both Si-H and C—H compounds can function as hydride donors under certain circumstances. The silicon-hydrogen bond is capable of transferring a hydride to carbo-cations. Alcohols that can be ionized in trifluoroacetic acid are reduced to hydrocarbons in the presence of a silane. 

Fig. 11. Models of neutralized substitutional boron in silicon. Hydrogen bonded to a) Si, b) B, c) bridging bond, and d) OH bonded to B.

Table I includes the relative bond dissociation enthalpies obtained for some group 14 hydrides by photoacoustic calorimetry,7 10 The data demonstrate that, for the trialkyl-substituted series, the bond strengths decrease by 6.5 and 16.5 kcal/mol on going from silane to germane and to stannane, respectively. The silicon-hydrogen bonds can be dramatically weakened by successive substitution of the Me3Si group at the Si-H functionality. A substantial decrease in the bond strength is also observed by replacing alkyl with methylthio groups.

The most complete mechanistic studies have been made with trisubstituted silanes, which initially undergo an exclusive silicon-hydrogen bond cleavage. Retention of configuration occurs in the ozonolysis of 1-decahydronaphthylcyclohexylmethylsilane 68 to the corresponding hydroxide ... 

Burger. P. and Bergman, R.G. (1993) Facile intermolecular activation of carbon-hydrogen bonds in methane and other hydrocarbons and silicon-hydrogen bonds in silanes with the iridium(III) complex Cp (PMe3)Ir (CH3)(OTf). J. Am. Chem. Soc., 115 (22). 10462-10463. 

Hydrosilylation, the addition of a silicon-hydrogen bond to multiple bonds, is a valuable laboratory and industrial process in the synthesis of organosilicon compounds. The addition to carbon-carbon multiple bonds can be accomplished as a radical process initiated by ultraviolet (UV) light, y irradiation, or peroxides. Since the discovery in the 1950s that chloroplatinic acid is a good catalyst to promote the addition, metal-catalyzed transformations have become the commonly used hydrosi-... 

None of these difficulties arise when hydrosilylation is promoted by metal catalysts. The mechanism of the addition of silicon-hydrogen bond across carbon-carbon multiple bonds proposed by Chalk and Harrod408,409 includes two basic steps the oxidative addition of hydrosilane to the metal center and the cis insertion of the metal-bound alkene into the metal-hydrogen bond to form an alkylmetal complex (Scheme 6.7). Interaction with another alkene molecule induces the formation of the carbon-silicon bond (route a). This rate-determining reductive elimination completes the catalytic cycle. The addition proceeds with retention of configuration.410 An alternative mechanism, the insertion of alkene into the metal-silicon bond (route b), was later suggested to account for some side reactions (alkene reduction, vinyl substitution).411-414... 

VII. Mechanism of Solvolysis of Reactive Silanes A. The Silicon-Hydrogen Bond... 

Certain reactions of silyl—alkali metal compounds, such as coupling of (CH3) (C6H5)3 BSiLi with appropriate chlorosilanes (51) and hydrolysis of [(CH3)3Si]3SiLi (63), lead to the formation of organopolysilanes with the silicon-hydrogen bond. There have been few reports of such synthesis. 

---