(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)bis(tert-butyloxy)germanium(II) | 1067499-07-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: (1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)bis(tert-butyloxy)germanium(II)
• CAS: 1067499-07-3
• 化学式: C₁₉H₃₈GeN₂O₂
• 分子量: 399.113
• InChiKey: PJSWSVVIWUXJDN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.82
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  24.94
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)bis(tert-butyloxy)germanium(II) 、 碘甲烷 以 苯 为溶剂， 以86%的产率得到[4,5-Dimethyl-1,3-di(propan-2-yl)imidazol-1-ium-2-yl]-methyl-bis[(2-methylpropan-2-yl)oxy]germane;iodide
  参考文献：
  名称：

  Reactivity Studies of N-Heterocyclic Carbene Complexes of Germanium(II)

  摘要：

  The chemistry of three N-heterocyclic carbene (NHC) complexes of GeR2, where R = Cl (1), (OBu)-Bu-1 (2), Mes (3) (Mes = 2,4,6-trimethylphenyl), toward 2,3-dimethylbutadiene (DMB), 3,5-di-tert-butylorthoquinone, methyl iodide, pivalic acid, and benzophenone is reported. Upon heating, 2 and 3 cyclize with DMB to yield a germacyclopentene and free NHC. In contrast, 1 does not react with DMB. PB1PBE/6-311+G(d,p) model chemistry shows that the cycloaddition reactions of NHC-GeX2 (X = F, Cl) with butadiene are not thermodynamically favorable. 3,5-Di-tert-butylorthoquinone reacts rapidly with 1-3 to form cyclic products; in the case of 1 and 2, the NHC remains coordinated to the germanium, resulting in a hypervalent species. Compounds 1-3 react with methyl iodide by displacement of in each case [NHC-GeR2Me](+) is produced. Only compound 3 reacts in a controlled fashion with pivalic acid; both 1:1 and 1:2 adducts were characterized. Benzophenone failed to react with 1 or 2 but did undergo cycloaddition with 3. In comparison with uncomplexed GeR2 species, the NHC-GeR2 complexes are less reactive. The prospect of using NHC-GeR2 as a synthon for GeR2 appears to be reaction specific.

  DOI：

  10.1021/om100059z
• 作为产物：
  描述：

  dichloro(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)germanium(II) 、 potassium tert-butylate 以 四氢呋喃 为溶剂， 以89%的产率得到(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)bis(tert-butyloxy)germanium(II)
  参考文献：
  名称：

  Synthesis and Structure of N-Heterocyclic Carbene Complexes of Germanium(II)

  摘要：

  The synthesis and structural characterization of a series of N-heterocyclic carbene (NHC) complexes of GeR1R2 are reported, where R-1 = R-2 = Mes (Mes = 2,4,6-trimethylphenyl) (1), R-1 = R-2 = F (5), R-1 = R-2 = Br (6), R-1 = Cl, R-2 = OTf (OTf = O3SCF3) (7), R-1 = R-2 = (OBu)-Bu-t (10), and R-1 = R-2 = NCS (11). The bond length between the carbenic carbon and the germanium is observed to vary in accordance with the pi-donating ability of the substituent on Ge. Efforts to synthesize stable complexes with small alkyl or aryl substituents were not successful; evidence for oligomerization of the GeR2 fragment is presented. The reaction between 1 and 3 (R-1 = R-2 = Cl) resulted in the formation of an NHC-coordinated germylgermylene (13). The H-1 NMR spectra of 3-7, 10, and 11 display broad signals at room temperature. To rationalize the H-1 NMR spectra, mechanisms for conformational interchange, as well as intermolecular exchanges, are discussed.

  DOI：

  10.1021/om800368d