7366-23-6Relevant academic research and scientific papers
Selective Chlorination of Germanium Hydrides
Hafner, Thomas,Torvisco, Ana,Traxler, Michael,Uhlig, Frank,Wolf, Melanie
, p. 1876 - 1881 (2020)
Methods for the selective chlorination of organogermylhydrides are given by the selective functionalization of organogermylhydrides of types R3GeH, R2GeH2 and RGeH3 (R = alkyl, aryl). The use of trichloroisocyan
Chromium carbonyl complexes with aryl mono- and oligogermanes: Ability for haptotropic rearrangement
Zaitsev, Kirill V.,Gloriozov, Igor P.,Oprunenko, Yuri F.,Lermontova, Elmira Kh,Churakov, Andrei V.
supporting information, p. 217 - 227 (2019/10/16)
The intra- and intermolecular inter-ring η6 ? η6-haptotropic rearrangements (IRHR), occurring by involving interactions to Ge atoms in arylgermanes, were investigated theoretically and experimentally. The new methods for the synthesis of non-symmetrical polyaromatic Ge compounds were elaborated. Digermane Ph3GeGeMe2Cl (2) was obtained from Ph3GeGeMe2NMe2 (1) under action of Me3SiCl. Aryl digermane Ph3GeGeMe2(η6-C6H5)Cr(CO)3 (4) was obtained after lithiation of (η6-C6H6)Cr(CO)3 (3) with subsequent interaction with 2. It was established that thermally induced intramolecular IRHR in 4 is not observed experimentally; at similar reaction conditions in the presence of tetralin C10H12 (7) the bimolecular intermolecular IRHR occurs giving (η6-C10H12)Cr(CO)3 (8). DFT analysis of the intramolecular IRHRs for model germane (p-Tol)2Ge(H)(η6-Tol-p)Cr(CO)3 (MC1) and digermane Ph3GeGeH2(η6-C6H5)Cr(CO)3 (MC2) indicates a plausible effect of 3c-2e (agostic) Ge–H···Cr interaction on success of such rearrangement. The theoretical activation barrier is determined to be in the range of 35–37 kcal/mol. The model compound (η6-C6H3(GeHPh2)Me2-p)Cr(CO)3 (12) was obtained from (η6-C6H4Me2-p)Cr(CO)3 (11). The decomposition of 12 was observed under conditions of thermally induced IRHR. Molecular structures of 8, 11 and 12 in a crystal were investigated by XRD.
A computational study of the fluctional behaviour of group 14 substituted ortho -semiquinone radicals
Ingold,Dilabio, Gino A.
, p. 235 - 240 (2011/04/23)
The dynamics of the 1,4-migration of some O-substituted 3,5-di-tert-butyl-ortho-semiquinone radicals have been calculated by density-functional theory (DFT). There is very good agreement in the rate constant and Arrhenius parameters between these calculations and experimental values for migration of H, D, and the Me3Si group. For the Me 3Sn group, the calculations indicate an incredibly fast migration (k293K = 2.0 × 1012 s-1), a result that is consistent with experimental data (k293K > 109 s-1). Other O-substituents examined by DFT and compared with experimental data were H3C and Me2ClSn.
Selective synthesis of chlorohydrogermanes from mono-, di-, and trihydrogermanes
Ohshita, Joji,Toyoshima, Yutaka,Iwata, Arihiro,Tang, Heqing,Kunai, Atsutaka
, p. 886 - 887 (2007/10/03)
Treatment of hydrogermanes, R4-nGeHn (R = Hex, Et, Ph, n = 1-3), with 2 equiv of CuCl2 in ether at room temperature or in toluene under reflux led to selective replacement of an H-Ge bond with a Cl-Ge bond, giving the corresponding chlorohydrogermanes, R4-nGeHn-1Cl, selectively.
New (diarylgermyl)lithiums
Castel,Riviere,Satge,Ko
, p. 205 - 210 (2008/10/08)
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.
ASSISTANCE NUCLEOPHILE DANS DES REACTIONS DE REDUCTION D'ORGANOHALOGENO- ET HALOGENO-GERMANES PAR DES REDUCTEURS DOUX R3M(IVB)-H ET RCHO: GERMYLANIONS, DERIVES FONCTIONNELS DU GERMANIUM
Castel, A.,Riviere, P.,Satge, J.
, p. 137 - 146 (2007/10/02)
Catalytic activity of nuclophiles such as tertiary amines and diazo derivatives in the reduction of halogermanes by means of gentle reductive agents, such as R3M(IVB)-H or RCHO, has been shown.In the particular case of enolisable aldehyde, a competition between nucleophilic substitution at the metal and germanium-halogen bond reduction has been observed.Transposition of enoxygermanes formed through the substitution process, leads to β-germylaldehydes.
