Halosilanes reactions with amines

The reaction of halosilanes with alcohols proceeds analogously. Dihinctional amines react with tetrahalosilanes to yield tetrakis(dialkylamino)silanes. 

Silyl alkyl and silyl aryl peroxides 7 are prepared by reaction of alkyl, aryl or aralkyl hydroperoxides with halosilanes (equation 12). Such reactions are carried out in an inert solvent in the presence of an acid acceptor, such as pyridine, ammonia or a tertiary amine in ether or petroleum ether (Table 3) . ... 

The reaction between aryl azides and lithiated aryl amines leads to tetrazenes, which give cyclic silatetrazenes with halosilanes (equation 7)17. Also, the new mono-, bis- and tris-silylamines 15-28 were obtained18-22. The hydrazine 16 was analyzed by electron and X-ray diffraction18. 

The reaction between halosilanes and ammonia or primary or secondary amines is the most widely used synthetic route to compounds containing 8i-N bonds. 8uch reactions are greatly controlled by steric effects if large groups are present on either the silicon or the amine, then less than full substitution may occur. For example, ammonia reacts with chlorosilanes to give a variety of products depending on the size of the chlorosilane (equation 32). 

Halosilanes are very reactive toward protic chemicals. They generally react violendy with water, forming silicon dioxide and the respective hydrohalogens. Other examples include reaction with alcohols and amines as follows ... 

Aminosilanes are valuable compounds in modem silicon chemistry, not only as alternative precursors for chemical vapor deposition of Si3N4, but also because of their many interesting chemical features. The amino groups can be easily attached to silicon by the reaction of halosilanes with amines or alkali metal amides using standard literature procedures [I ]. 

Disilathianes, for example (SiH3)2S and [(CH3)3Si] 2S, have been prepared by several routes, namely, the reaction of iodosilane with silver8 and mercuric2 sulfides halosilanes with lithium sulfide,7 [NH4]SH,9 and [Me3NH]SH7 disilaselenane with H2S10 and trisilylphosphine with sulfur.10 Recently, the synthesis of hexamethyldisilathiane, [(CH3)3Si] 2S, was described from the protolysis of l-(trimethylsilyl)imidazole with H2S and from the dehydrohalogen-ation of chlorotrimethylsilane and H2S with a tertiary amine.11 Both of these methods require about 18 hours. 

In continuation of these studies it is our aim to apply similar reaction sequences to higher linear and cyclic halosilanes. Thus partially aminated products are easily accessible by the reaction of linear chlorosilanes Si Cl2 + 2 or cyclic chlorosilanes Si Cl2n with one or more equivalents of LiN(TMS)2. The maximum number of bis(trimethylsilyl)amino groups which can be attached to the corresponding silicon backbones is examined, as well as the hydrogenation of the resulting products. 

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