tetrakis(germyl)methane | 77742-44-0

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: tetrakis(germyl)methane
• 英文别名: Methanetetrayltetrakis(germane)；trigermylmethylgermane
• CAS: 77742-44-0
• 化学式: CH₁₂Ge₄
• 分子量: 314.466
• InChiKey: LSEZXVRIHPFILP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -4.52
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  Methanetetrayltetrakis[tribromogermane] 在 LiAlH₄ 、 benzyltriethylammonium chloride 作用下， 以 further solvent(s) 为溶剂， 以20%的产率得到tetrakis(germyl)methane
  参考文献：
  名称：

  Novel Methods for CVD of Ge₄C and (Ge₄C)_xSi_y Diamond-like Semiconductor Heterostructures:  Synthetic Pathways and Structures of Trigermyl-(GeH₃)₃CH and Tetragermyl-(GeH₃)₄C Methanes

  摘要：

  GeX2.dioxane (X = Cl, Br) complexes insert completely into CBr4 to afford the sterically crowded cluster compounds (BrCl2Ge)(4)C (1) and (Br3Ge)(4)C (2) in 80% and 95% yields, respectively. These display physical, spectroscopic, and structural properties that are indicative of highly symmetric molecules with a remarkably strained carbon center. Compounds 1 and 2 react with LiAlH4 to produce the hydrides (H-3 Ge)(3)CH (3) and (H3Ge)(4)C (4) which an readily identified and characterized by spectroscopic methods and gas-phase electron diffraction. Compound 3 is also conveniently prepared from the LiAlH4 reduction of (GeBr3)(3)CH (5) which in turn is obtained by insertion of GeBr2.dioxane into the C-Br bonds of bromoform. Refinement of the diffraction data for 3 confirmed a model of C-3 symmetry, with local (3 upsilon) symmetry of the GeH3 groups, and gave a Ge-C bond length of 1.96 Angstrom. The structure refinement of 4 was based on a model of T symmetry and displayed a rather normal Ge-C bond distance of 1.97 Angstrom, which is substantially shorter than that (2.049 Angstrom) of the strained (Br3Ge)(4)C (2) compound. Density functional calculations closely reproduced the observed molecular structures for 3 and 4. The thermal dehydrogenation of 4 on (100) Si surfaces at 500 degrees C resulted in the growth of a diamond-structured material with an approximate composition of Ge4C. Reactions of 4 with (SiH3)(2) on Si yielded heteroepitaxial growth of metastable, monocrystalline (Ge4C)(x)Si-y alloy semiconductors that are intended to have band gaps wider than those of pure Si and Si1-xGex alloys and strained superlattices. The covalent cluster species described here not only are of intrinsic molecular interest but also provide a unique route to a new class of semiconductor materials and form a model for local carbon sites in Ge-C crystals and related electronic materials based on the diamond structure.

  DOI：

  10.1021/ja9810033

文献信息

• Synthesis and Characterization of Tetrakis(trihalogermyl)methanes. Molecules Containing Sterically Strained Carbon Centers
  作者：Phillip T. Matsunaga、John Kouvetakis、Thomas L. Groy

  DOI：10.1021/ic00125a004

  日期：1995.10

  Dihalogermylene complexes, GeX(2) . dioxane (X = Cl, Pr), undergo complete insertion into CBr4 to afford the sterically crowded tetrakis(trihalogermyl)methanes, (BrCl2Ge)(4)C (1) and (Br3Ge)(4)C (2). Compounds 1 and 2 display physical properties and IR spectra indicative of highly symmetric molecules containing a tetrahedral core of group IVA atoms. An X-ray analysis of 2 indicates that carbon centers can exist in sterically strained germanium environments (e.g. the cubic lattice of Ge1-xCx alloys) without fragmenting. Both 1 and 2 react with LiAlH4 to produce the reduction products (H3Ge)(4)C (3) and (H3Ge)(3)CH (4), thus completing the family of silyl- and germylmethanes, (H(3)M)(4-x)CHx (M = Si, Ge; x = 0-3).
• Novel Methods for CVD of Ge₄C and (Ge₄C)<i>_x</i>Si<i>_y</i> Diamond-like Semiconductor Heterostructures:  Synthetic Pathways and Structures of Trigermyl-(GeH₃)₃CH and Tetragermyl-(GeH₃)₄C Methanes
  作者：J. Kouvetakis、Arne Haaland、Dmitry J. Shorokhov、Hans Vidar Volden、Georgii V. Girichev、Vasili I. Sokolov、Phillip Matsunaga

  DOI：10.1021/ja9810033

  日期：1998.6.13

  GeX2.dioxane (X = Cl, Br) complexes insert completely into CBr4 to afford the sterically crowded cluster compounds (BrCl2Ge)(4)C (1) and (Br3Ge)(4)C (2) in 80% and 95% yields, respectively. These display physical, spectroscopic, and structural properties that are indicative of highly symmetric molecules with a remarkably strained carbon center. Compounds 1 and 2 react with LiAlH4 to produce the hydrides (H-3 Ge)(3)CH (3) and (H3Ge)(4)C (4) which an readily identified and characterized by spectroscopic methods and gas-phase electron diffraction. Compound 3 is also conveniently prepared from the LiAlH4 reduction of (GeBr3)(3)CH (5) which in turn is obtained by insertion of GeBr2.dioxane into the C-Br bonds of bromoform. Refinement of the diffraction data for 3 confirmed a model of C-3 symmetry, with local (3 upsilon) symmetry of the GeH3 groups, and gave a Ge-C bond length of 1.96 Angstrom. The structure refinement of 4 was based on a model of T symmetry and displayed a rather normal Ge-C bond distance of 1.97 Angstrom, which is substantially shorter than that (2.049 Angstrom) of the strained (Br3Ge)(4)C (2) compound. Density functional calculations closely reproduced the observed molecular structures for 3 and 4. The thermal dehydrogenation of 4 on (100) Si surfaces at 500 degrees C resulted in the growth of a diamond-structured material with an approximate composition of Ge4C. Reactions of 4 with (SiH3)(2) on Si yielded heteroepitaxial growth of metastable, monocrystalline (Ge4C)(x)Si-y alloy semiconductors that are intended to have band gaps wider than those of pure Si and Si1-xGex alloys and strained superlattices. The covalent cluster species described here not only are of intrinsic molecular interest but also provide a unique route to a new class of semiconductor materials and form a model for local carbon sites in Ge-C crystals and related electronic materials based on the diamond structure.