- 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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- 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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- Facile central-element exchange in neutral hexacoordinate germanium and silicon complexes; Synthesis and characterization of germanium complexes
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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
- Yakubovich, Shiri,Kalikhman, Inna,Kost, Daniel
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- Direct synthesis of organotrichlorogermanes by the reaction of elemental germanium, hydrogen chloride, and alkene
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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.
- Okamoto, Masaki,Chikamori, Takehiko,Asano, Takuya,Suzuki, Eiichi
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- The chlorination equilibrium of germanium oxides
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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.
- Rau, Hans
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- Reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride
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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.
- Zhun,Sbitneva,Polivanov,Chernyshev
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- SO2 effect on GeO2 chlorination
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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.
- Vinokurova,Derlyukova
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p. 1321 - 1324
(2008/10/09)
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- Thermal transformations of phenyltrichlorogermane in the gas phase
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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.
- Chernyshev,Komalenkova,Yakovleva,Bykovchenko,Khromykh,Bochkarev,Shcherbinin
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p. 1406 - 1409
(2007/10/03)
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- Synthesis, structures and properties of N-(trihalogermylmethyl)-substituted amides, lactams and imides, the derivatives of the five-coordinate germanium
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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
- Gar, T. K.,Dombrova, O. A.,Ivashchenko, D. A.,Mironov, V. F.
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p. 1717 - 1723
(2007/10/02)
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- Reactivity of Sulphuryl Chloride in Acetonitrile with the Elements
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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.
- Woolf, Alfred A.
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p. 3325 - 3330
(2007/10/02)
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- Stabilization of the first selenogermylene as the monomeric pentacarbonyltungsten(0) complex
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Bis[(2,4,6-tri-tert-butylphenyl)seleno]germylene, formed in situ by reaction of lithium 2,4,6-tri-tert-butylphenyl selenide with the germanium dichloride dioxane complex, was trapped as the monomeric pentacarbonyl[bis((2,4,6-tri-tert-butylphenyl)seleno)germylene]tungsten(0) complex. Reaction of bis-(2,4,6-tri-tert-butylphenyl) diselenide with the germanium dichloride dioxane complex provides dichlorobis((2,4,6-tri-tert-butylphenyl)seleno)germane. This tetravalent germanium compound and bis-(2,4,6-tri-tert-butylphenyl) diselenide were identified as byproducts when preparation and isolation of the monomeric selenogermylene was attempted. The structure of the selenogermylene tungsten(0) complex was determined from single-crystal X-ray diffraction data. The complex crystallizes (with one toluene per molecule) in the monoclinic space group P21/c with a = 1077.4 (2), b = 1667.2 (2), c = 2880.9 (2) pm, β = 98.33°, and Z = 4. The molecule contains trigonal planar germanium with bonds to tungsten and to two nonequivalent selenium atoms (Ge-Se, 231.4 (2) and 234.6 (2) pm; Ge-W, 252.8 (1) pm). Well-resolved 1H, 13C, and 77Se NMR signals for the two (2,4,6-tri-tert-butylphenyl)seleno groups of the selenogermylene complex indicate hindered rotation around the Ge-Se bonds at room temperature in solution.
- Du Mont, Wolf-W.,Lange, Lutz,Pohl, Siegfried,Saak, Wolfgang
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p. 1395 - 1399
(2008/10/08)
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- Chemistry of Germanium Atoms. II. Reactions of Thermally Evaporated Germanium Vapor with Organic Halides
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Thermally generated germanium atoms were found to react with organic halides by insertion into carbon-halogen bonds.The resulting germylenes abstracted halogens from organic halides to form trihalogermyl derivatives.Tetrahalogermanes were also formed by t
- Mochida, Kunio,Tashiro, Kumiko,Yoshida, Yasuhiro,Mizuno, Yasuhisa
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p. 1247 - 1250
(2007/10/02)
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- Chemistry of Germanium Atoms. IV. A New Method for Preparation of Organogermanium Halides by Co-condensation of Germanium Vapor with Tetrahydrofuran
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Germanium vapor (atom) when co-condensated with THF at 77 deg K was found to be reactive toward organic halides.Several organogermanium halides were prepared by the addition of organic halides to the resultant germanium atom-THF slurry at ambient temperatures.
- Mochida, Kunio,Nakai, Yuko,Shiota, Shigeru
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p. 3002 - 3004
(2007/10/02)
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- The Reaction of Germanium Atoms with Organic Halides
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Co-condensation of thermally evaporated germanium vapor with organic halides yields a mixture of trihalogermyl derivatives and tetrahalogermanes as major products.The nature of these reactions is discussed.
- Mochida, Kunio,Tashiro, Kumiko
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p. 1105 - 1108
(2007/10/02)
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- ZUR CHEMIE VON t-BUTYLGERMANIUM-HALOGENIDEN UND -CHALKOGENIDEN
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Upon reaction with an excess of t-C4H9Li GeCl4 gives 2 (I) and with 2 equivalents of t-C4H9Li it gives (t-C4H9)2GeCl2 (II) together with rearranged and condensated products (III, IV, V) and polycondensates.The reaction with 3 molar equivalents of t-C4H9Li gives predominantly (t-C4H9)3GeCl (VI) with a minor amount of I.Also (t-C4H9)2GeH2 (VII) could be isolated.In the presence of triethylamine from the reaction of II with H2S, (t-C4H9)2Ge(SH)2 (VIII) is obtained, which readily condenses to give cyclotetra-t-butyl-1,3-dithia-2,4-digermane (IX).IX can be also obtained in high yields from the reaction of I and sulfur, and from II and KHS in the presence of 18-crown-6, with cyclotetra-t-butyl-1,2,4-trithia-3,5-digermane (X) as a byproduct.X is the main product in the reaction of II and H2S in the presence of imidazole.From I and selenium or tellurium the corresponding 4-membered ring compounds XI and XII are obtained, with the 5-membered ring compound XIII as a byproduct of the reaction with selenium.The compounds are characterized spectroscopically (MS, 1H-NMR, and partly IR) and for those which have been separated in a pure state also by analyses.An X-ray structure determination has been performed for IX.
- Wojnowska, Maria,Noltemeyer, Mathias,Fuellgrabe, Hans-Juergen,Meller, Anton
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p. 229 - 238
(2007/10/02)
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- Complexation and Exchange Reactions of some Dimethylamino-substituted Group 4 Compounds
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Reactions of CH2(NMe2)2, (1), SiMe2(NMe2)2, (2), (cp=η-cyclopentadienyl), (3), and , (4), with covalent metal halides MCl4 (M=Ti,Zr,Si,Ge,or Sn) and MCl3 (M=Ti,V,or Cr) fall into two categories: (a) N-donor chelation leading to complex formation and (b) halide-NMe2 exchange.Compound (1) gives 1:1 complexes with MCl4 (M=Ti or Sn) and 2:1 complex with VCl3.Compound (2) provides 1:1 complexes with MCl4 (M=Ti,Zr,Hf, or Sn).The decomposition of TiCl4*SiMe2(NMe2)2 --> invariably occurs in both the solid state and solution.There is no reaction of (2) with metal(III) chlorides.With MCl4 (M=Si or Ge 'scrambling' reactions involving halide-NMe2 exchange occur and these have been monitored by 1H n.m.r. spectroscopy.Reactions of (3) and (4) with MCl4 (M=Si,Ge,Sn,Ti,Zr,or Hf) consistently feature halide-NMe2 exchange rather than adduct formation.All complexes have been characterised by analytical and spectroscopic (1H n.m.r. and i.r.) investigations.
- Wade, Steven R.,Willey, Gerald R.
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p. 1264 - 1267
(2007/10/02)
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