993-62-4Relevant academic research and scientific papers
Use of neodymium diiodide in the synthesis of organosilicon, -germanium and -tin compounds
Balashova, Tatyana V.,Kusyaev, Dmitry M.,Kulikova, Tatyana I.,Kuznetsova, Olga N.,Edelmann, Frank T.,Giessmann, Stephan,Blaurock, Steffen,Bochkarev, Mikhail N.
, p. 256 - 260 (2008/10/09)
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
Molecular hydrides of samarium and europium LnH2(THF)2 (Ln = Sm or Eu): Synthesis and properties
Fedorova,Trifonov,Kirillov,Bochkarev
, p. 946 - 948 (2007/10/03)
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)
A radical mechanism of the reaction of molybdenum carbonyl complexes with bis(triethylgermyl)mercury
Sykhrannova, M. I.,Tatarnikov, A. N.,Khorshev, S. Ya.,Gladyshev, E. N.
, p. 1585 - 1587 (2007/10/02)
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.
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.
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.
Photochemical Addition of Benzyltriethylgermane and Dibenzyldiethylgermane to Olefines
Kobayashi, Masanori,Yoshida, Masato,Kobayashi, Michio
, p. 3169 - 3174 (2007/10/02)
A novel photochemical addition of a germanyl radical to the olefinic double bond was discovered when benzyltriethylgermane or dibenzyldiethylgermane was irradiated with a medium-pressure mercury lamp in the presence of olefins.
REACTIONS OF TRIETHYLGERMYLLITHIUM WITH N,N-DIALKYLATED CARBOXAMIDES
Bravo-Zhivotovskii, D. A.,Pigarev, S. D.,Kalikhman, I. D.,Vyazankina, O. A.,Vyazankin, N. S.
, p. 51 - 60 (2007/10/02)
The reactions of triethylgermyllithium with N,N-dialkylated carboxamides have been investigated.N,N-Dimethylacetamide, N,N-dimethylpivalamide, N,N-diethyltrifluoroacetamide and N,N-diethylbenzamide act on triethylgermyllithium, which is made from bis(triethylgermyl)mercury and lithium in hexane, to release the corresponding acyltriethylgermanes as the principal product.The regioselectivity of the present reactions was found to depend markedly on the reaction conditions and the nature of the acyl fragment of amides.Thus, triethylgermyllithium reacts with N,N-dimethylacetamide as metallating agent to give lithium N,N-dimethylacetamide, if the reaction is carried out in tetrahydrofuran solution.Mechanistic interpretations of these results are discussed.
