597-63-7Relevant academic research and scientific papers
Direct electrochemical synthesis of germanium alkoxides
Vereshchagin,Elinson,Krylova,Novikov,Egorov
, p. 464 - 465 (2015/10/29)
Anodic galvanostatic dissolution of germanium in alcohols in an undivided cell in the presence of trace amounts of NaOAc as an electrolyte afforded germanium alkoxides with a current efficiency of 88-95%.
Process for the preparation of group IVA and group VIA compounds
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Page 10, (2008/06/13)
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.
ETUDE DE REACTIONS PAR TRANSFERT MONOELECTRONIQUE ENTRE DIVERS HYDROGERMANES A CARACTERE ACIDE ET DES SYSTEMES QUINONIQUES DIA- ET PARA-MAGNETIQUES
Riviere, P.,Castel, A.,Abdennadher, C.
, p. 181 - 194 (2007/10/02)
The chlorogermanes PhnCl3-nGe-H (n = 0, 1, 2) were treated with diamagnetic (3,5-di-t-butylorthoquinone) 1 and the paramagnetic galvinoxyl 2.These reactions occur mainly by monoelectron transfer giving the corresponding adducts.In the case of 3,5-di-t-butylorthoquinone, the resulting 1-4 adducts decompose by two simultaneous processes (HCl elimination and redistribution) yielding germadioxolanes.The chlorogermadioxolanes prepared in this way easily cause halogenic redistribution leading to chlorogermanes and germylcatecholates having branched or spiranestructure.In the case of the galvinoxyl radical, the same chlorogermanes lead by monoelectron transfer to the corresponding quinophenol and an intermediate germanium-centered radical.The latter by recombination outside the solvent cage, gives digermane.However, its primary reaction, which occurs within the solvent cage, is with quinophenol to form two isomeric O- and C-germylated catechols.The C-isomer is by far predominant as it also formed in the secondary hydrogermylation of quinophenol produced in the initial stage of the reaction.We have been able to confirm these mechanisms by a comparative study of the reaction of germanium hydrides R3Ge?+-H?-, acidic germanes X3Ge?--H?+, and germanates X3Ge(-)N-H(+) with galvinoxyl and the corresponding quinophenol.Key words: SET reactions; germylations; quinones; chlorohydrogermanes; chlorogermanes; chlorogermanates.
Reactivity of dianionic hexacoordinate germanium complexes toward organometallic reagents. A new route to organogermanes
Cerveau,Chuit,Corriu,Reyé
, p. 1510 - 1515 (2008/10/08)
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.
The effect of substituents on the structure and reactivity of organogermanium anions
Pigarev, S. D.,Bravo-Zhivotovskii, D. A.,Kalikhman, I. D.,Vyazankin, N. S.,Voronkov, M. G.
, p. 29 - 42 (2007/10/02)
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.
Reactions of nucleophilic reagents with dianionic hexacoordinated germanium complexes: A new convenient route to functional organogermanes from germanium dioxide
Cerveau,Chuit,Corriu,Reye
, p. 786 - 787 (2008/10/08)
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.
REACTIONS DE GERMYLENES AVEC DES HETEROCYCLES A TROIS CHAINONS. MISE EN EVIDENCE D'ESPECES TRICOORDINEES DU GERMANIUM R2Ge=X (X = O,S) ET DE NOUVEAUX GERMYLENES FONCTIONNELS
Barrau, Jacques,Bouchaut, Marsan,Lavayssiere, Helene,Dousse, Gabriel,Satge, Jacques
, p. 281 - 290 (2007/10/02)
Condensations of complexed dialkylgemylenes R2Ge*NEt3 with various oxiranes and thiirane gave, by insertion and ring expansion, the corresponding oxa- and thia-germacyclobutanes (X=O, S).These thermally unstable heterocycles led via β-eliminations to transient dialkylgermanones and germathiones which, by insertion into oxirane and thiirane (excess) formed germadioxolanes and germadithiolanes.Dialkylgermylenes did not react with N-substituted aziridine.Dichlorogermylene reacted with aziridine under formation of aziridinogermylene, while it formed complexes with N-ethylaziridine.Cleavages of aminogermylenes and insertion reactions of complexed dichlorogermylene are described.Dialkylgermylenes insert into the O-H of methanol leading to dialkylmethoxygermanes R2Ge(H)OMe.
The reaction of ethylene with digermane: ethylpolygermanes
Mackay,Watt
, p. 123 - 129 (2007/10/06)
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,
