2816-38-8Relevant academic research and scientific papers
Syntheses, structures, and electronic properties of the branched oligogermanes (Ph3Ge)3GeH and (Ph3Ge) 3GeX (X = Cl, Br, I)
Samanamu, Christian R.,Amadoruge, Monika L.,Yoder, Claude H.,Golen, James A.,Moore, Curtis E.,Rheingold, Arnold L.,Materer, Nicholas F.,Weinert, Charles S.
, p. 1046 - 1058 (2011/04/25)
The branched oligogermanium hydride (Ph3Ge)3GeH was synthesized via a hydrogermolysis reaction from GeH4 and Ph 3GeNMe2 and was converted to the halide series of compounds (Ph3Ge)3GeX (X = Cl, Br, I) upon reaction with [Ph3C][PF6] in CH2X2 solvent (X = Cl, Br, I). These species were fully characterized by NMR (1H and 13C) and UV/visible spectroscopy, cyclic voltammetry, and elemental analysis. In addition, (Ph3Ge)3GeH was analyzed by 73Ge NMR spectroscopy and exhibits two resonances at δ -56 and -311 ppm. A Ge-H coupling constant of 191 Hz was observed in the proton-coupled 73Ge NMR spectrum of (Ph3Ge)3GeH. The X-ray crystal structures of (Ph3Ge)3GeH and (Ph 3Ge)3GeX (X = Cl, Br, I) were obtained and represent the first examples of branched oligogermane hydrides or halides to be characterized in this fashion. The Ge-Ge bond distances in (Ph3Ge)3GeH are short (average value 2.4310(5) A), while those in the halide compounds (Ph3Ge)3GeX are similar to one another and range from 2.4626(7) to 2.4699(5) A. The UV/visible and cyclic voltammetry data for these species have been correlated with DFT computations, and excellent agreement was found between the experimental and theoretical data.
Preparation, structure, and reactivity of discrete branched oligogermanes
Amadoruge, Monika L.,Golen, James A.,Rheingold, Arnold L.,Weinert, Charles S.
, p. 1979 - 1984 (2009/02/01)
The hydrogermolysis reaction of PhGeH3 serves in the synthesis of discrete branched oligogermanes. Treatment of PhGeH3 with 3 equiv of the α-germyl nitriles R3GeCH2CN (R3 = Ph3 or Bu2CH2CH2OEt), which are generated in situ from the corresponding amides R3GeNMe2 and CH3CN, furnishes the tetragermanes PhGe(GePh3) 3 and PhGe(GeBu2CH2CH2OEt) 3 in excellent yield. The crystal structure of PhGe(GePh 3)3 was determined. This compound is the first branched oligogermane to be structurally characterized. Reaction of the tetragermane PhGe(GeBu2CH2CH2OEt)3 with Bu i2AlH generated the intermediate hydride PhGe(GeBu 2H)3. Subsequent treatment of PhGe(GeBu2H) 3 with the synthons R2Ge(NMe2)CH 2CH2OEt (R = Bu, Et, Ph) in CH3CN solution furnished the heptagermanes PhGe(GeBu2GeR2CH 2CH2OEt)3 (R = Bu, Et, Ph). The latter process also proceeds through the in situ formation of the α-germyl nitriles R2Ge(CH2CN)CH2CH2OEt.
