Dehydrosilylation

Dehydrosilylation reaction. While the dehalosilylation reaction is very powerful for the synthesis of Ga—Sb and In—Sb heterocycles, this reaction type completely failed for the synthesis of the corresponding stibinoalanes. Only the reaction of Me2AlCl with Sb(Tms)3, leading to the formation of [Me(Gl)AlSb(Tms)2]3 38, yielded an Al—Sb heterocycle [36a]. However, 38 obviously was not formed by dehalosilylation but by tetramethylsilane elimination reaction (Scheme 9). 

Scheme 11. Initial dehydrosilylation reactions as performed by Noth et al., Fritz et al. and Krannich et al.

Dehydrosilylation versus oxidative addition of enol silyl ethers to quinones... 

Scheme 9. Formation of heterocyclic stibino- and bismuthinoalanes by dehydrosilylation...

Dative bonding, 229 Decamethylmetallocenes, 1-2, 6, 8-9, 20 of silicon see Decamethylsilicocene Decamethylsilicocene, 1-34 chemistry of, 9-31 structure, 4-7 synthesis, 3 1 Decomposition betaines, 37-38, 78-87 thiobetaines, 57-63, 65 for film deposition, 304-306 Dehalosilylation reaction, 260-262 Dehydrosilylation reaction, 262-264 Density functional theory (DFT), 177 Deposition, film, 257-258, 265, 301-303 DFT (density functional theory), 177 Diazasilole derivatives, decamethylsilicocene gives, 24-25... 

Table 4 Heterocyclic stibinoalanes of the type [R2AlSbR 2]x synthesized by dehydrosilylation reaction ...

Ga - Sb heterocycles can also be synthesized by the dehydrosilylation reaction, whereas the lack of stable dialkylindanes R2lnH inhibited the synthesis of In - Sb heterocycles, to date. 

The most striking feature of this reaction type is the simple formation of completely alkyl-substituted M - Sb heterocycles, which are hardly accessible by dehalosilylation and dehydrosilylation reactions due to the tendency of silylsubstituted dialkylstibines R2SbSiMe3 to undergo ligand exchange reactions at elevated temperatures, leading to the synthesis of partially silylsubstituted hetero cycles [28]. 

A number of disilanes have been investigated for their suitability as potential silene precursors. The formation of silenes by the 1,3-silyl migration pathway competes with dehydrosilylation, which also gives silenes, and with homolytic Si—Si bond cleavage to give silyl radicals. 

In the case of the disilane 244 1,3-silyl migration to give silene 245 competes with dehydrosilylation to give silene 2461411 (equation 61). 

Dehydrosilylation occurs in the reaction of H3Ga NMe3 with As(SiMc3)3 to provide an efficient route to [(Me3Si)2-AsGaH2]3. ... 

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