[2]tetramethyldisilacobaltocenophane | 1085965-00-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [2]tetramethyldisilacobaltocenophane
• 英文别名: [(Me4Si2(η5-C5H4)2))Co]；cobalt(2+);cyclopenta-2,4-dien-1-yl-[cyclopenta-2,4-dien-1-yl(dimethyl)silyl]-dimethylsilane
• CAS: 1085965-00-9
• 化学式: C₁₄H₂₀CoSi₂
• 分子量: 303.477
• InChiKey: AYRRRNPVNZETAI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.73
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ferrocenium hexafluorophosphate 、 [2]tetramethyldisilacobaltocenophane 以 二氯甲烷 为溶剂， 以92%的产率得到[(Me4Si2(η5-C5H4)2))Co]PF6
  参考文献：
  名称：

  Synthesis, Crystal Structure, EPR and DFT Studies, and Redox Properties of [2]Tetramethyldisilacobaltocenophane

  摘要：

  The first [2]silacobaltocehophane, [(Me2Si)(2)(eta(5)-C5H4)(2)Co] (1), was synthesized by dilithiation of 1,2-bis(cyclopentadienyl)-1,1,2,2-tetramethyldisilane with BuLi and subsequent reaction with [CoBr2(dme)]. EPR spectroscopic investigations of frozen pentane solutions of 1 at X-band showed a fully anisotropic g tensor (g(1) = 1.914, g(2) = 2.005, and g(3) = 2.084) with hyperfine couplings on all three components (A(1) = 145 MHz, A(2) = 67 MHz, and A(3) = 424 MHz). DFT studies using the B3LYP functional with its 20% exact exchange provide the best agreement with experiment and reproduce the g and A tensors well. Spin-orbit contributions to the isotropic coupling (A(PC)) and to the anisotropies (A(i)(dip,2)) were found to be significant. As was shown by cyclic voltammetry in THF, 1 is quasi-reversibly oxidized to the neutral cobaltocenium cation [(Me2Si)(2)(eta(5)-C5H4)(2)Co](+) (8) at a potential of E-1/2 degrees = -1.27 V (vs the Fc/Fc(+) couple) and quasi-reversibly reduced to the corresponding anion [(Me2Si)(2)(eta(5)-C5H4)(2)Co](-) (9) at E-1/2 degrees = -2.40 V. The preparative oxidation of 1 with 1 equiv of feffocenium hexafluorophosphate ([Fc][PF6]) provided the diamagnetic [PF6](-) salt of the cation 8 in high yields. The molecular structures of both complexes (1 and 8) were confirmed by X-ray diffraction analysis, and a significant decrease in molecular strain was depicted. DFT findings support the experiments.

  DOI：

  10.1021/om8003724
• 作为产物：
  描述：

  cobalt dibromide*1,2-dimethoxyethane 、 C5H4(SiMe3)(SiMe2CHCHCH3)) 在 CH₃CH₂CH₂CH₂Li 作用下， 以 四氢呋喃 为溶剂， 以31%的产率得到[2]tetramethyldisilacobaltocenophane
  参考文献：
  名称：

  Synthesis, Crystal Structure, EPR and DFT Studies, and Redox Properties of [2]Tetramethyldisilacobaltocenophane

  摘要：

  The first [2]silacobaltocehophane, [(Me2Si)(2)(eta(5)-C5H4)(2)Co] (1), was synthesized by dilithiation of 1,2-bis(cyclopentadienyl)-1,1,2,2-tetramethyldisilane with BuLi and subsequent reaction with [CoBr2(dme)]. EPR spectroscopic investigations of frozen pentane solutions of 1 at X-band showed a fully anisotropic g tensor (g(1) = 1.914, g(2) = 2.005, and g(3) = 2.084) with hyperfine couplings on all three components (A(1) = 145 MHz, A(2) = 67 MHz, and A(3) = 424 MHz). DFT studies using the B3LYP functional with its 20% exact exchange provide the best agreement with experiment and reproduce the g and A tensors well. Spin-orbit contributions to the isotropic coupling (A(PC)) and to the anisotropies (A(i)(dip,2)) were found to be significant. As was shown by cyclic voltammetry in THF, 1 is quasi-reversibly oxidized to the neutral cobaltocenium cation [(Me2Si)(2)(eta(5)-C5H4)(2)Co](+) (8) at a potential of E-1/2 degrees = -1.27 V (vs the Fc/Fc(+) couple) and quasi-reversibly reduced to the corresponding anion [(Me2Si)(2)(eta(5)-C5H4)(2)Co](-) (9) at E-1/2 degrees = -2.40 V. The preparative oxidation of 1 with 1 equiv of feffocenium hexafluorophosphate ([Fc][PF6]) provided the diamagnetic [PF6](-) salt of the cation 8 in high yields. The molecular structures of both complexes (1 and 8) were confirmed by X-ray diffraction analysis, and a significant decrease in molecular strain was depicted. DFT findings support the experiments.

  DOI：

  10.1021/om8003724