- Chemical Vapour Deposition of Germanium Films by Laser-induced Photolysis of Ethylgermanes
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Excimer laser photolysis of ethylgermanes EtnGeH4-n (n = 1-4) at 193 nm yields ethane, ethene and butane along with germanium deposited on the inner surface of the reactor.The distribution of gaseous products is remarkably different
- Pola, Josef,Parsons, Jonathan P.,Taylor, Roger
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- Investigation of the reaction of bis(triethylgermyl)cadmium with titanium tetrachloride
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The reaction between (Et3Ge)2Cd and TiCl4 in the presence of α,α'-bipyridyl afforded a compound with a Ge-Cd-Ti group.This compound was characterized by IR and ESR spectroscopy.Thermal decomposition of this compound at 130 and 160 deg C and its interaction with gaseous HCl were studied.A novel complex, (Et3Ge)2Cd*bpy, was obtained as a by-product of the reaction, and some its physicochemical characteristics were determined.Based on the experimental results, a scheme for the interaction of (Et3Ge)2Cd with TiCl4 has been suggested. - Key words: mixed organo-Cd, Ti compounds.
- Lomakova, I.V.,Patrikeeva, N. B.,Domrachev, G. A.,Petrov, B. I.
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- The reaction of ethylene with digermane: ethylpolygermanes
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Ethylene reacts directly with digermane at 120-160° and 5-10 atm pressure to yield not only digermanes, EtnGe2H6-n, but also monogermanes and trigermanes. Ethyldigermane and the new compounds 1,1- and 1,2-diethyldigermane,
- Mackay,Watt
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- REDUCTION OF ALKOXYSILANES, HALO-SILANES AND -GERMANES WITH LITHIUM ALUMINIUM HYDRIDE UNDER PHASE-TRANSFER CONDITIONS
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In the presence of phase-transfer catalysts, silicon and germanium organohydrides were obtained in high yield by reduction of the corresponding halo and alkoxy derivatives with lithium aluminium hydride in the solid LiAlH4/hydrocarbon two-phase system.
- Gevorgyan, V. N.,Ignatovich, L. M.,Lukevics, E.
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- R3E+ carborane salts of the heavier group 14 elements: E = Ge, Sn, and Pb
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The synthetic and structural chemistry of catalytically useful trialkylsilylium salts with weakly coordinating carborane anions, R 3Si(CHB11X11), has been extended to the heavier group 14 elements. Et3Ge(CHB11H5Br 5) was prepared from Et3GeH and trityl CHB 11H5Br6-. Its X-ray crystal structure shows ion-like character very similar to its Si congener. The heavier element analogues, Et3E(CHB11H5Br6) (E = Sn, Pb), were prepared by chloride ion abstraction from Et3SnCl and Et3PbCl, respectively, using Et3Si(CHB 11H5Br6). Their crystal structures differ from those of the four-coordinate lighter elements by adopting five-coordinate trigonal-bipyramidal stereochemistries, reflecting the periodic table transition of these elements from semi-metals to metals. The carborane anions are weak, bridging, axial ligands connecting trigonal Et3E+ cation-like moieties in polymeric chain structures. When the less coordinating CHB11Cl11- anion is used, excess germane competes with the carborane anion for coordination to Ge and a salt of the new hydride-bridged cation [Et3Ge-H-GeEt3]+ can be isolated. It has a distinctive αGeHGe IR band at ca. 1740 cm-1 analogous to the 1875 cm-1 band of the [Et3Si-H-Si-Et 3]+ cation. Comparable chemistry is not observed for the Sn and Pb congeners.
- Wright, James H.,Mueck, Gabriel W.,Tham, Fook S.,Reed, Christopher A.
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- Use of neodymium diiodide in the synthesis of organosilicon, -germanium and -tin compounds
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The reactivity of neodymium diiodide, NdI2 (1), towards organosilicon, -germanium and -tin halides has been investigated. Compound 1 readily reacts with Me3SiCl in DME to give trimethylsilane (6 %), hexamethyldisilane (4 %) and (Mes
- Balashova, Tatyana V.,Kusyaev, Dmitry M.,Kulikova, Tatyana I.,Kuznetsova, Olga N.,Edelmann, Frank T.,Giessmann, Stephan,Blaurock, Steffen,Bochkarev, Mikhail N.
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- Access to Fully Alkylated Germanes by B(C6F5)3-Catalyzed Transfer Hydrogermylation of Alkenes
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Various cyclohexa-2,5-dien-1-yl-substituted germanes are shown to serve as easy-to-handle surrogates of hydrogermanes, including gaseous MeGeH3 and Me2GeH2. The Ge-H functional group is liberated by treatment with catalytic amounts of B(C6F5)3 and participates in situ in the B(C6F5)3-catalyzed hydrogermylation of alkenes. The range of suitable alkenes is broad, and the overall procedure provides a convenient access to tetraalkyl-substituted germanes at room temperature. Transfer hydrogermylation of internal alkynes works equally well and selectively forms the trans or cis diastereomer depending on the electronic bias of the C≡C bond.
- Keess, Sebastian,Oestreich, Martin
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supporting information
p. 1898 - 1901
(2017/04/11)
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- Syntheses of di- and trinuclear platinum complexes with multibridged germanium centers derived from unsymmetrical digermanes
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A trigonal-bipyramidal Pt3Ge2 cluster was synthesized by the reaction of the zerovalent platinum complex [Pt(dppe)(η2- C2H4)] (dppe = 1,2-bis(diphenylphosphino)ethane) with the unsymmetrical digermane H3GeGeEt3 at a 3/2 molar ratio. The platinum centers formed a triangular plane bridged by two germylyne ligands, one of which maintained the Ge-Ge bond. To investigate the Pt 3Ge2 cluster formation process, the phenyl-substituted digermanes HPh2GeGeMe3 and H2PhGeGeR 3 (R = Me, Et), in which two hydrogen atoms and one hydrogen atoms of the reactive GeH3 moiety were replaced by the bulkier phenyl group(s) together with the substitution of the GeEt3 group by a GeMe3 group, respectively, were used to simplify the reaction system. They provided the digermylplatinum hydride [Pt(dppe)(H)(GePh 2GeMe3)] (2) and the bis(μ-germylene)diplatinum complexes [Pt2(dppe)2(μ-GeHPh)(μ-Ge(Ph)GeR 3)] (3, R = Me; 4, R = Et) in moderate yields, respectively. For 3 and 4, the first-formed digermylplatinum hydride I-1 underwent dissociation of one of the phosphorus donors followed by 1,2-germyl migration to give the corresponding bis(germyl)platinum complex I-2, as observed in the previously reported silicon system. On the one hand, the germyl migration did not take place in the case of 2, owing the Ge-Ge bond being less reactive than the Si-Si bond. Intermediates I-1 and I-2 coupled to each other to afford the germylene-bridged diplatinum complexes 3 and 4 accompanied by extrusion of H2 and R3GeH. In the case of H3GeGeEt 3, the corresponding bis(μ-germylene)diplatinum complex reacted with [Pt(dppe)(η2-C2H4)], resulting in the formation of the desired Pt3Ge2 cluster. The spiro-type Pt4Ge complex was obtained only by changing mole equivalents of [Pt(dppe)(η2-C2H4)], demonstrating the usefulness of the present method using H3GeGeEt3, which can readily regulate the molar ratio.
- Arii, Hidekazu,Hashimoto, Rei,Mochida, Kunio,Kawashima, Takayuki
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p. 6635 - 6641
(2012/11/07)
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- Reaction of organoelement hydrides R3EH (E = Si, Ge) with metal tert-butylate (M = Al, Ti)-tert-butyl hydroperoxide oxidative systems
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Trialkyl(aryl)silanes and -germanes effectively react with metal (Al, Ti) tert-butylate-tert-butyl-hydroperoxide under mild conditions (room temperature, benzene or tetrachloromethane) mainly by the element-hydrogen bond. The character of the products depends on the nature of the element, the structure of the radical bound to it, and the solvent. The process is radical in nature. It includes the stages of formation of element-centered radicals and their reaction with the oxygen generated by the system. The intermediate organometallic peroxides can also acts as oxidants for the element (Si, Ge)-hydrogen bonds. 2005 Pleiades Publishing, Inc.
- Stepovik,Gulenova,Martynova,Skvortsov,Cherkasov
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p. 1098 - 1107
(2007/10/03)
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- Molecular hydrides of samarium and europium LnH2(THF)2 (Ln = Sm or Eu): Synthesis and properties
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The molecular hydrides Ln11H2(THF)2(Ln = Sm or Eu) were prepared by hydrogenolysis of the naphthalene complexes of divalent samarium and europium C10H8Ln(THF)2 (Ln = Sm or Eu, respectively)
- Fedorova,Trifonov,Kirillov,Bochkarev
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p. 946 - 948
(2007/10/03)
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- The Germanium-Carbon Bond Cleavage Reaction of (Germylmethyl)amine Derivatives. Mechanism and Stereochemistry
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A facile cleavage reaction of the germanium-carbon bond of (germylmethyl)amine derivatives to give a germyl anion and an azomethine derivative was developed.The effects of substituents such as phenyl, benzyl, and ethyl groups on the germanium and nitrogen atoms of the (germylmethyl)amine derivatives on the cleavage reaction were investigated.The mechanism was also investigated based on the stereochemistry of the cleavage reaction using an optically active organogermanium compound.
- Terunuma, Daiyo,Masuo, Koujiro,Kizaki, Hiroaki,Nohira, Hiroyuki
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p. 160 - 164
(2007/10/02)
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- A radical mechanism of the reaction of molybdenum carbonyl complexes with bis(triethylgermyl)mercury
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The reaction of 2 with (Et3Ge)2Hg occurs in toluene and THF by a radical mechanism.The interaction between 2Hg and (Et3Ge)2Hg has a radical character only in THF.The formation of Cp(CO)3MoH at the first stage of these reactions substantially affects the further course of the process.
- Sykhrannova, M. I.,Tatarnikov, A. N.,Khorshev, S. Ya.,Gladyshev, E. N.
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p. 1585 - 1587
(2007/10/02)
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- Reactivity of dianionic hexacoordinate germanium complexes toward organometallic reagents. A new route to organogermanes
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Lithium and potassium tris(benzene-1,2-diolato)germanates (2a and 2b, respectively) and potassium tris(butane-2,3-diolato)germanate (3) are easily prepared from GeO2 in quantitative yields. They are very reactive toward organometallic reagents, the reactivity depending on the ligands on the germanium. Complexes 2 react with an excess of Grignard reagent to give the corresponding tetraorganogermanes R4Ge while the less reactive complex 3 leads to the functional triorganogermanes R3GeX. Tetraorganogermanes can also be prepared from complex 2b by reaction with organic bromides in the presence of Mg (Barbier reaction). The influence of Cp2TiCl2 and MgBr2 on the reactivity of Grignard reagents with these complexes was also investigated: in both cases formation of triorganogermanes was favored.
- Cerveau,Chuit,Corriu,Reyé
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p. 1510 - 1515
(2008/10/08)
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- The Ge-H bond dissociation energies of organogermanes. A laser-induced photoacoustic study
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The Ge-H bond dissociation energies (BDE's) of several alkyl- and aryl-substituted germanium hydrides have been measured in hydrocarbon solution at room temperature by a photoacoustic technique. The BDE's of these hydrides are unaffected by alkyl substitution when compared to those for GeH4 and are in the range of 81.6-82.6 kcal/mol. Aryl substitution leads to a slightly weakened Ge-H bond (79.2-80.2 kcal/mol) in the cases of phenyl-, diphenyl-, and triphenylgermane. In an effort to further characterize the formation, spectral and decay properties of the germyl radicals some laser flash photolysis studies were carried out. The rate constants for hydrogen abstraction by tert-butoxy radicals were determined by nanosecond laser flash photolysis and fell in the range (0.7-4.4) × 108 M-1 s-1. The aryl-substituted germyl radicals add to the aromatic rings of the germane precursor. Diphenylgermyl radical adds to diphenylgermane with a rate constant of 2.9 × 105 M-1 s-1, while phenylgermyl radical adds to phenylgermane with a rate constant of 1.2 × 106 M-1 s-1.
- Clark, K. Brady,Griller, David
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p. 746 - 750
(2008/10/08)
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- New (diarylgermyl)lithiums
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The new (diarylgermyl)lithiums R2GeHLi (2; R = phenyl, mesityl) were prepared in good yields by hydrogermolysis reactions of tert-butyllithium in THF. The stability of compounds 2 depends on the nature of the R group and the solvent. For R = Ph, in the presence of an amine (Et3N or Et2NMe), the same reaction leads to the formation of the polygermanes H(GePh2)nH (n = 2-4). The characterization of compounds 2 by IR and 1H and 13C NMR spectroscopy and their complexation with a crown ether are also reported. They are characterized by deuterolysis and alkylation reaction (with MeI and Me2SO4). Their germylation reactions with Ge-Cl reagents constitute a convenient way for synthesizing organo-hydropolygermanes. Compounds 2 also react with acyl chlorides to give new germyl ketones, R2HGeCOR′, and the unexpectedly stable β-germyl diketone Ph2Ge(COMes)2.
- Castel,Riviere,Satge,Ko
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p. 205 - 210
(2008/10/08)
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- The effect of substituents on the structure and reactivity of organogermanium anions
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The replacement of the ethyl group in Et3GeH by a phenyl group was shown by equilibrium metallation to halve the pKa value compared with analogous CH acids.NMR showed that the decreased acceptor effect of the phenyl group in the PhEt2Ge- anion is caused by a considerably reduced contribution of the mesomeric effect to anion stabilization compared with what happens in the corresponding carbanions.At the same time, the stabilization of the organogermanium anion increases the role of ?-polarization of the aromatic substituent and this contribution is comparable with the mesomeric effect value.A stabilizing effect of organosilicon and organogermanium substituents due to a high degree of polarizability has been shown by concurrent methanolysis of Et3GeLi and REt2GeLi (R=Me3Si, Et3Si, Me3Ge, Et3Ge, t-Bu, Ph).An unexpected reaction of the trimethylsilyl anion with the Me3SiGeEt2- anion leading to diethylgermane dianion, Et2Ge2- has been revealed.The existence of this process supports the suggested absence of (d-p)? interaction in germanium anions with organo-silicon and -germanium substituents.
- Pigarev, S. D.,Bravo-Zhivotovskii, D. A.,Kalikhman, I. D.,Vyazankin, N. S.,Voronkov, M. G.
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- Reactions of nucleophilic reagents with dianionic hexacoordinated germanium complexes: A new convenient route to functional organogermanes from germanium dioxide
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Tetraorganogermanes and triorganogermanes can be prepared in two steps from GeO2: the preparation of the anionic hexacoordinated germanium complexes followed by reaction of these with Grignard reagents to give the organogermanes.
- Cerveau,Chuit,Corriu,Reye
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p. 786 - 787
(2008/10/08)
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- THERMAL DECOMPOSITION OF ORGANO-BIELEMENTAL VANADIUM COMPOUNDS Cp2V(ER3) (ER3 = GeEt3, SnEt3, CH2SiMe3, SeGeEt3)
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The thermal decomposition of a number of organo-bielemental vanadium compounds with the general formula Cp2V(ER3) (ER3 = GeEt3, SnEt3, CH2SiMe3, SeGeEt3) has been investigated in solids and in solutions.The main decomposition products of Cp2V(SnEt3) are vanadocene and hexaethyldistannane.Et3GeH, Et3GeCp, Cp2V and CpV(C5H4GeEt3) are formed from Cp2V(GeEt3) decomposition.Isolated CpV(C5H4GeEt3) is characterized by IR and mass spectra.The decomposition of Cp2V(CH2SiMe3) is accompanied by Me4Si, Cp2V and CpV(C5H4CH2SiMe3) formation, the latter is identified from the mass spectrum.Triethylgermane, vanadocene, and a diselenide of vanadium are isolated on decomposition of Cp2V(SeGeEt3).Based upon the experimental data, mechanisms for the decomposition are proposed.
- Razuvaev, G. A.,Latyaeva, V. N.,Mar'in, V. P.,Vyshinskaya, L. I.,Korneva, S. P.,et al.
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p. 233 - 244
(2007/10/02)
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