Bond cleavage hydrogen-silicon

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 ... 

Replacements of one or two chlorine atoms and hydrogen by fluorine were observed in various organosilicon compounds in reactions with xenon difluoride99,135, while aryl-silicon bond cleavage was observed in the presence of potassium fluoride136,137 (Scheme 57). 

Price, Fr. P. Mechanism of the Alkaline Cleavage of Silicon-Hydrogen Bonds ... 

Hydroxylic solvents are able to promote heterolytic Si-X bond cleavage (X =F or Cl) (1, 268). The kinetics have been studied extensively and the activation of the reaction by an additional nucleophile has been observed (268, 269, 341, 342). A mechanism, involving an increase of the nucleophilicity of the alcohol by hydrogen bonding, has been proposed (Scheme 63) (103,341). Alternatively, a pentacoordinate intermediate has been invoked (1,342) (Scheme 64). Discrimination between the two above interpretations has recently been provided good evidence for the nucleophilically induced process at silicon has been presented (268,269,343). 

Silicon-hydrogen bonds also add to dinuclear complexes in reactions that are formally one-electron oxidative additions, or simply metal-metal bond cleavage reactions. The reaction of dicobalt octacarbonyl with an excess of silane leads to silylcobalt carbonyls (equation 13)2 3. Similar reactions involving Mn-Mn29, Re-Re30, Fe-Fe31, Ru-Ru32,... 

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