Reactions of Radicals with Silicon Hydrides

Although we will deal with organic radicals in solution, it is worth mentioning that the reactivity of atoms and small organic radicals with silanes in the gas phase has been studied extensively. For example, the bond dissociation energies of a variety of Si-H bonds are based on the reaction of iodine or bromine with the corresponding silanes.1 

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 

The kinetic data for reactions of carbon-centered radicals with various silanes and the silanthrane derivatives 1-6 are numerous as shown in 

Rate Constants for Reactions of Carbon-Centered Radicals with Silicon Hydrides 

Silane Radical Solvent Rate constant (M 1 s 4) (temp in °C as subscript) Rate expression (log k) (e = 2.3RT kcal/mol) Ref. 

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Table 3.2 Rate constants for the reactions of radicals with silicon hydrides...

The reaction of radicals with silicon hydrides is the key step for the majority of reactions forming silyl radicals (equation 19). All available rate constants and activation parameters for reaction 19 have been recently collected and discussed together with those... 

The reaction of thiyl radicals with silicon hydrides (Reaction 8) is the key step of the so-called polariiy-reversal catalysis in the radical chain reduction. The reaction is strongly endothermic and reversible with alkyl-substituted silanes (Reaction 8). For example, the rate constants fcsH arid fcgiH for the couple triethylsilane/ 1-adamantanethiol are 3.2 x 10 and 5.2xlO M s respectively. 

The reactions of atoms or radicals with silicon hydrides, germanium hydrides, and tin hydrides are the key steps in formation of the metal-centered radicals [Eq. (1)]. Silyl radicals play a strategic role in diverse areas of science, from the production of silicon-containing ceramics to applications in polymers and organic synthesis.1 Tin hydrides have been widely applied in synthesis in radical chain reactions that were well established decades ago.2,3 Germanium hydrides have been less commonly employed but provide some attractive features for organic synthesis. 

The kinetic data for reactions of nitrogen-centered radicals with silicon hydrides is limited to rate constants for piperidinyl radical 18 (Table IV) by using ESR spectroscopy.61 The two remarkable features of the data are... 

Table 3.3 Rate constants (25 °C) and Arrhenius parameters for the reactions of aminyl radicals with silicon hydrides [21,22] ...

The reaction of thermally and photochemically generated tcrt-butoxyl radicals with silicon hydrides (Reactions 3.13 and 3.14) has been extensively used for the generation of silyl radicals in EPR studies, time-resolved optical techniques, and organic synthesis. 

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-... 

As with silicon hydrides, the reaction of atoms or radicals with germanium hydrides is the key step for the majority of reactions forming germyl radicals. However, kinetic data for the reactions of organic radicals with germanium hydrides in solution are limited to carbon- and oxygen-centered radicals. 

The reaction of atoms, radicals or excited triplet states of some molecules with silicon hydrides is the most important way for generating silyl radicals [1,2]. Indeed, Reaction (1.1) in solution has been used for different applications. Usually radicals X are centred at carbon, nitrogen, oxygen, or sulfur atoms... 

Formation of a siloxane network via hydrosilylation can also be initiated by a free-radical mechanism (300-302). A photochemical route makes use of photosensitizers such as peresters to generate radicals in the system. Unfor-timately, the reaction is quite sluggish. Several complexes of platinum such as (jj-cyclopentadienyl)trialkylplatinum(rV) compoimds have been found to be photoactive. The mixture of silicone polymer containing alkenyl functional groups with silicon hydride cross-linker materials and a catalytic amoimt of a cy-clopentadienylplatinum(IV) compound is stable in the dark. Under UV radiation, however, the platinum complex imdergoes rapid decomposition with release of platinum species that catalyze rapid hydrosilylation and network formation (303-308). Other UV-active hydrosilylation catalyst precursors include (acetylacetonate)Pt(CH3)3 (309), (acetylacetonate)2Pt (310-312), platinum tri-azene compounds (313,314), and other sytems (315,316). 

The hydrogen abstraction from the Si-H moiety of silanes is fundamentally important for these reactions. Kinetic studies have been performed with many types of silicon hydrides and with a large variety of radicals and been reviewed periodically. The data can be interpreted in terms of the electronic properties of the silanes imparted by substituents for each attacking radical. In brevity, we compared in Figure 1 the rate constants of hydrogen abstraction from a variety of reducing systems by primary alkyl radicals at ca. 80°C. ... 

This review focuses on the kinetics of reactions of the silicon, germanium, and tin hydrides with radicals. In the past two decades, progress in determining the absolute kinetics of radical reactions in general has been rapid. The quantitation of kinetics of radical reactions involving the Group 14 metal hydrides in condensed phase has been particularly noteworthy, progressing from a few absolute rate constants available before 1980 to a considerable body of data we summarize here. 

PhSeSiRs reacts with BusSnH under free radical conditions and affords the corresponding silicon hydride (Reaction 1.8) [19,20]. This method of generating RsSi radicals has been successfully applied to hydrosilylation of carbonyl groups, which is generally a sluggish reaction (see Chapter 5). 

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