di(methoxo)tetraphenylporpyrinatogermanium | 55988-54-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: di(methoxo)tetraphenylporpyrinatogermanium
• 英文别名: tppGe(OMe)2；dimethoxo(meso-tetraphenylporphyrinato)germanium(IV)
• CAS: 55988-54-0
• 化学式: C₄₆H₃₄GeN₄O₂
• 分子量: 747.392
• InChiKey: GVYWTYJIYUADHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  chloro(meso-tetraphenylporphyrinato)germanium(IV) 在 Al₂O₃ 作用下， 以 氯仿 为溶剂， 生成 di(methoxo)tetraphenylporpyrinatogermanium
  参考文献：
  名称：

  Crystal structures of chloro(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)Cl2, and dihydroxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OH)2, and two-stage hydrolysis of its homologue dimethoxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OMe)2

  摘要：

  The crystal structures of chloro(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)Cl-2, dimethoxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OMe)(2), and dihydroxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OH)(2), were determined. The coordination sphere of the Ge4+ ion is a distorted octahedron in which the apical sites are occupied by two monodentate Cl- (or OMe- OH-) groups. The geometry around the germanium centre of the Ge(tpp)Cl-2 molecule has Ge(1)-Cl(1) = 2.262(1) and Ge(1)-N(1) = 2.019(2) Angstrom. In the structure of Ge(tpp)(OMe)(2) the germanium(1)-oxygen distance is 1.826(3), average Ge(I)-N = 2.032(3), and O(1)-C(23) = 1.331(6) Angstrom. The structure of Ge(tpp)(OH)(2) has Ge(1)-O(1) = 1.809(3) and Ge(I)-N(I) - 2.027(2) Angstrom., Two-stage hydrolysis of Ge(tpp)(OMe)(2) was studied by H-1 and C-13 NMR spectroscopy. The use of a limited amount of water in CDCl3 (or CD2Cl2) allowed the hydrolysis intermediate, hydroxomethoxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OMe) (OH), and hydrolysis product, dihydroxo(meso-tetraphenylporphyrinato) Ge(tpp)(OH)(2), to be identified, X-ray diffraction data and solid-state C-13 CP/MAS spectra of Ge(tpp)(OMe)(2) provide evidence for two monodentate methoxo groups coordinated to the germanium(IV) atom. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0277-5387(97)00011-9

文献信息

• <font>C</font>–<font>H</font> bond activation with <font>Ge</font>-oxyl complex generated by photoinduced-electron-transfer of di(hydroxo)porphyrin <font>Ge</font>^{<font>IV</font>} complex
  作者：Tsutomu Shiragami、Ayano Kuroki、Jin Matsumoto、Masahide Yasuda

  DOI：10.1142/s1088424614500345

  日期：2014.7

  electron transfer from 31a* to Fe 3+ or K 2 PtCl 6 to generate porphyrin radical cation (1a+•), which underwent a proton dissociation of hydroxo axial ligand to give tpp ( OH ) Ge - O • ( Ge -oxyl complex) as key intermediate. The Ge -oxyl complex oxidized substrates through a hydrogen-atom abstraction. It is strongly suggested that 1a can act as a good sensitizer for being able to activate C – H bond

  可见光照射含有二（羟基）四苯基卟啉和锗（IV）络合物（ tppGe ( OH ) 的甲醇溶液2; 1a)、异丙苯和 Fe3+离子 ( Fe ( NO3)3) 作为电子受体产生枯醇作为氧化产物和 Fe2+离子作为还原产物。量子产率（Φ牛) 和形成枯醇的翻转频率 (TOF) 分别为 0.033 和 111.1 h-1， 分别。将 KOH 水溶液 (1 mM) 添加到反应溶液中导致 Φ 增加牛至 0.047。电子从激发三重态转移的自由能变化 (ΔG) (31a*) 到 Fe3+估计为一个很大的负值（-1.37 eV）。此外，在 K 存在下，MeOH 的 1a-光敏氧化2氯化铂6作为电子受体，甲醛 ( HCHO ) 在 Φ 中形成牛= 0.034 和 TOF = 120.0 小时-1. HCHO 形成的同位素效应 (Φ氧(H)/Φ牛(D)= 5.04) 在 MeOH -d 时观察到4被用作基板。在