Dehalosilylation reaction

Dehalosilylation reaction. The dehalosilylation reaction was introduced by Wells et al. in 1986, who obtained arsinogallanes by reaction of R2AsTms with chlorogallanes under elimination of TmsCl [68] (Scheme 7). 

Scheme 7. First synthesis of Ga—As compounds by dehalosilylation reaction...

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). 

Other synthetic pathways for the preparation of group-13-element antimony compounds include dehydro- and dehalosilylation reactions of R2SbSiMe3 or Sb(SiMe3)3 with R MX or MX3 (R = SiMe3, t-Bu R = Me, Et, i-Bu M = Ga, In X = H, Cl).53 A review of the chemistry of these potential precursors for 13-15 semiconductors was recently published.55... 

Wells et al. introduced the dehalosilylation reaction for the synthesis of group 13/15 compounds in 1986. Reactions between silylarsines of the type R/AsSiMe3 with chlorogallanes occurred with elimination of Me3SiCl, leading to the formation of arsinogallanes of the types [Cl2GaAsR2]x79 (Scheme 6). 

Scheme 6. Wells initial studies on the synthesis of arsinogallanes by dehalosilylation reaction.

Scheme 7. Synthesis of heterocyclic stibinogallanes and -indanes by dehalosilylation reaction.

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... 

In the last decade, this so-called dehalosilylation reaction was shown to be generally applicable for the synthesis of four- and six-membered Ga - Sb and In - Sb heterocycles as summarized in Table 3 [19,24]. 

Tables Heterocyclic stibinogallanes and -indanes of the type [R2MSb(SiMe3)2]x (M = Ga, In) synthesized by dehalosilylation reaction...

Amidocarbonylation aldehydes, 11, 512 enamides, 11, 514 overview, 11, 511-555 Amido complexes with bis-Cp titanium, 4, 579 Group 4, surface chemistry on oxides, 12, 515 Group 5, surface chemistry on oxides, 12, 524 with molybdenum mono-Cp, 5, 556 with mono-Cp titanium(IV) alkane elimination, 4, 446 amine elimination, 4, 442 characteristics, 4, 413 via dehalosilylation reactions, 4, 448 HCL elimination, 4, 446 metathesis reactions, 4, 438 miscellaneous reactions, 4, 448 properties, 4, 437... 

The tertiary arsines easily form adducts with the aluminum alkyls. The reaction of R2AICI (R = Me, i-Bu) with As[SiMc3]3 does not lead to a dehalosilylation reaction, but yields the adducts R2(Cl)AlAs[SiMe3]3. The other known As-Al bonded compounds are base-stabilized monomeric arsinoalanes and the cycloarsinoalanes. Although a few secondary arsines react with aluminum alkyls to give the cycloarsinoalanes (equations 34 and 35),6s,66,70 1 2-elimination route to arsinoalanes becomes... 

Relatively few germylarsines are known. They are usually prepared from the respective sUylarsine by a salt elimination or dehalosilylation reaction (equations 53-55). Cleavage of the Ge-N bond with a secondary arsine also leads to the formation of germylarsines (equation 56). Oxidation of the germylarsines with oxygen leads to the respective metal arsinates, R3Ge-0-As(0)R2. 

The amido ligand is isoelectronic with the alkyl and alkoxo groups and has the possibility to exhibit N-M ir-interactions in order to stabilize the systems they form. Different synthetic reactions are used to prepare mono-Cp titanium derivatives containing amido ligands. These compounds are normally synthesized by (i) the action of the corresponding amide salt on Cp TiCl3, (ii) displacement of amine from a homoleptic amido titanium compound by a Cp reagent, (iii) dehalosilylation reactions, and (iv) elimination of alkane by reaction of an alkyltitanium compound with amine. 

Fig. 10 Hydrogen elimination, alkane elimination, salt metathesis, and dehalosilylation reactions Table 4 Selected bond lengths (A) and angles (°) for heterocyclic stibidoalanes and bismuthi-...

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