- Organotrichlorogermane synthesis by the reaction of elemental germanium, tetrachlorogermane and organic chloride via dichlorogermylene intermediate
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Organotrichlorogermanes were synthesized by the reaction of elemental germanium, tetrachlorogermane and organic chlorides, methyl, propyl, isopropyl and allyl chlorides. Dichlorogermylene formed by the reaction of elemental germanium with tetrachlorogermane was the reaction intermediate, which was inserted into the carbon-chlorine bond of the organic chloride to give organotrichlorogermane. When isopropyl or allyl chloride was used as an organic chloride, organotrichlorogermane was formed also in the absence of tetrachlorogermane. These chlorides were converted to hydrogen chloride, which subsequently reacted with elemental germanium to give the dichlorogermylene intermediate. The reaction of elemental germanium, tetrachlorogermane and organic chlorides provides a simple and easy method for synthesizing organotrichlorogermanes, and all the raw materials are easily available.
- Okamoto, Masaki,Asano, Takuya,Suzuki, Eiichi
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p. 2372 - 2376
(2007/10/03)
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- Process for the preparation of group IVA and group VIA compounds
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Methods of preparing Group IVA and Group VIA organometallic compounds, particularly Group IVA organometallic compounds, are provided. Such manufacturing methods employ an amine and/or phosphine catalyst in a transalkylation step and may be performed in a batch, semi-continuous or continuous manner.
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- Gas-Phase Synthesis of Alkylchlorogermanes
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The major product of the hexachlorodisilane-initiated reaction of MeCl with GeCl4 at 500 and 550°C is MeGeCl3. The reactions of AlkSiCl3 (Alk=Me, Et) with GeCl4 at 550 50°C not produce (Alk=Me) or produce (Alk=Et) AlkGeCl3; a mechanism of formation of the latter is proposed.
- Chernyshev, E. A.,Komalenkova, N. G.,Yakovleva, G. N.,Bykovchenko, V. G.,Khromykh, N. N.,et al.
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- Formation of Halide Complexes of Methyl- and Inorganic Germanium(IV) in Aqueous Hydrohalogenic Acid Solutions
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The reaction of methyl- and inorganic germanium(IV) hydroxides ((CH3)nGe(OH)4-n; n = 1, 2, or 3) with halide ions (X = Cl-, Br-, or I-) to form halide complexes ((CH3)nGeX4-n) in aqueous acidic solution has been investigated by liquid-liquid extraction, solid-liquid distribution (ion exchange), and 1H NMR spectrometry.It has been found that methylgermanium moieties are hard Lewis acids similarly to inorganic germanium(IV), because the stability constant of the halide complexes decreases in the order Cl- > Br- > I-.The stability constant for an X- ion increases as the number of methyl groups attached to the germanium atom increases.The species of inorganic-, monomethyl-, and dimethylgermanium are nonionic and have a tetrahedral structure in HX solution, and OJ- ions attached to the germanium atom are stepwise substituted by X- ions with an increase in HX activity.Trimethylgermanium alone forms a cation, when the activity of HX is not sufficiently high.These facts suggest that the transfer of a negative charge from methyl groups to the central germanium atom lowers the stability of the bond between the germanium atom (hard acid) and an OH- ion (hard base).
- Sohrin, Yoshiki
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p. 3363 - 3371
(2007/10/02)
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- Tetramethylsilane in synthesis: Selective mono- and polymethylations of germanium tetrachloride
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In the presence of catalytic amounts of aluminum bromide (or chloride), selective mono-, di-, tri-, or tetramethylation of germanium tetrachloride was effected in high yield with tetramethylsilane (Me4Si) as the methylating reagent. According to the Me4Si/GeCl4 ratio, MeGeCl3, Me2GeCl2, Me3GeCl, and Me4Ge were prepared in 66, 86, 100, and 91% maximum yields, respectively. In these reactions, Me4Si was converted into Me3SiCl and subsequently Me2SiCl2. A mechanism for methylation is proposed, involving the initial formation of Me4Ge (observed regardless of the proportions of starting reagents) followed by disproportionation reactions, with methylchlorosilanes or -germanes present when the initial molecular ratio Me4Si/GeCl4 was lower than 4/1.
- Bordeau, Michel,Djamei, S. Mohammad,Dunoguès, Jacques
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p. 1087 - 1089
(2008/10/08)
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