10038-98-9Relevant articles and documents
Organotrichlorogermane synthesis by the reaction of elemental germanium, tetrachlorogermane and organic chloride via dichlorogermylene intermediate
Okamoto, Masaki,Asano, Takuya,Suzuki, Eiichi
, p. 2372 - 2376 (2004)
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.
Formation of Halide Complexes of Methyl- and Inorganic Germanium(IV) in Aqueous Hydrohalogenic Acid Solutions
Sohrin, Yoshiki
, p. 3363 - 3371 (1991)
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).
Facile central-element exchange in neutral hexacoordinate germanium and silicon complexes; Synthesis and characterization of germanium complexes
Yakubovich, Shiri,Kalikhman, Inna,Kost, Daniel
, p. 9241 - 9244 (2010)
Neutral hexacoordinate germanium complexes with hydrazido chelating ligands have been synthesized and characterized. Facile exchange of central element between silicon and germanium in these complexes is demonstrated, following given selectivity constrain
Direct synthesis of organotrichlorogermanes by the reaction of elemental germanium, hydrogen chloride, and alkene
Okamoto, Masaki,Chikamori, Takehiko,Asano, Takuya,Suzuki, Eiichi
, p. 595 - 599 (2004)
The reaction of elemental germanium, hydrogen chloride, and ethylene with copper(I) chloride catalyst gave ethyltrichlorogermane with a 66% selectivity, tetrachlorogermane also being formed. The addition of tetrachlorogermane to the reaction system increased the formation rate of ethyltrichlorogermane. The reaction of germanium, tetrachlorogermane, and butadiene resulted in the formation of 1,1-dichlorogermacyclopent-3-ene. These results indicate the intermediacy of dichlorogermylene, which is formed by the reaction of elemental germanium with tetrachlorogermane. In place of ethylene, allyl chloride was fed with hydrogen chloride. Allyltrichlorogermane was obtained with a 92% selectivity together with a small amount of tetrachlorogermane. It is highly plausible that the formation of allyltrichlorogermane is caused by the insertion of dichlorogermylene intermediate to the carbon - chlorine bond of allyl chloride.
The chlorination equilibrium of germanium oxides
Rau, Hans
, p. 287 - 294 (1984)
The reactions of tetragonal, hexagonal, and glassy GeO2 with chlorine were studied.From the measured equilibrium constants a third-law standard molar enthalpy of formation: ΔHf(GeCl4, g, 298.15 K, p0 = 101.325 kPa) = -(494.8 +/- 2.7) kJ*mol-1 was determined.
Reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride
Zhun,Sbitneva,Polivanov,Chernyshev
, p. 1564 - 1570 (2006)
The effect of substituents at the silicon and germanium atoms in reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride was studied. The only occurring process is the exchange of the chlorine atoms at Ge for the phenyl groups from Si; an increase in the number of methyl groups or chlorine atoms at Si promotes formation of phenyltrichlorogermane, and an increase in the number of phenyl groups or replacement of the chlorine atom at the Si atom by hydrogen leads to the formation of di-and triphenylchlorogermanes. Neither phenyl nor other radicals are transferred back from Ge to Si in the course of reactions of phenylgermanes with methylchlorosilanes in the presence of aluminum chloride; the only occurring processes are the exchange of the phenyl or methyl radicals bonded to Ge for the Cl atom bonded to Al and the disproportionation of phenylchlorogermanes. Nauka/Interperiodica 2006.
SO2 effect on GeO2 chlorination
Vinokurova,Derlyukova
, p. 1321 - 1324 (2008/10/09)
The SO2 effect on the interaction of amorphous GeO2 with gaseous Cl2 in the temperature range 600-875°C is studied. The GeO2 chlorination rate in the presence of SO2 increases over the entire temperature range. The process rate is described as a function of temperature by a curve with a maximum at 720°C, which is due to the partial transition of amorphous GeO2 to the hexagonal phase.
Thermal transformations of phenyltrichlorogermane in the gas phase
Chernyshev,Komalenkova,Yakovleva,Bykovchenko,Khromykh,Bochkarev,Shcherbinin
, p. 1406 - 1409 (2007/10/03)
Pyrolysis of PhGeCl3 and its mixtures with allyl chloride and isoprene in the temperature range 500-680°C was investigated. PhGeCl3 vigorously decomposes at temperatures higher 600°C, and its decomposition involves both dichlorogermylenes and trichlorogermyl radical. Pyrolysis of mixtures of PhGeCl3 with isoprene or allyl chloride yields respectively trichloro(1,2-dimethyl-2-propenyl)germane, isopentyltrichloro germanes, and 1,1-dichloro-3-methyl-1-germacyclo-3-pentene or allyltrichlorogermane. A mechanism of formation of these products is proposed.
Synthesis, structures and properties of N-(trihalogermylmethyl)-substituted amides, lactams and imides, the derivatives of the five-coordinate germanium
Gar, T. K.,Dombrova, O. A.,Ivashchenko, D. A.,Mironov, V. F.
, p. 1717 - 1723 (2007/10/02)
The formation of trichlorogermyl-substituted amides, lactams, and imides occurs when 2Et2O*HGeCl3 is condensed with compounds possessing the -NCH2Cl fragment and equally well when HGeCl3 interacts with compounds containing -NCH2OH and -NCH2OSiMe3 groups.I
Reactivity of Sulphuryl Chloride in Acetonitrile with the Elements
Woolf, Alfred A.
, p. 3325 - 3330 (2007/10/02)
Sulphuryl chloride in MeCN reacts with all but the most refractory elements to give mainly solvated chlorides at or below 300 K in contrast with SO2Cl2 alone which requires at least twice this temperature.There is evidence for an ionic mechanism based on analogy, thermochemistry, transport measurements and additive effects.The instability of these solutions leading to polymerization, together with its inhibition, is described.Sulphur dioxide formed in reactions seldom plays a reductive role apart from influencing formation of the mixed-valence Tl4Cl6.Semiquantitative kinetic measurements in different solvents emphasize the uniqueness of MeCN.For most elements attack is diffusion controlled across surface films giving a parabolic dependence on time which can be linearized if film growth is prevented by changing the solvent mix.The varied nature of these surface films vitiates any simple relation between rate and periodicity.Some applications are indicated.