[Cr(μ-Cl)(μ-OSi(t)Bu3)]4 | 851625-19-9

• 英文名称: [Cr(μ-Cl)(μ-OSi(t)Bu3)]4
• CAS: 851625-19-9
• 化学式: C₄₈H₁₀₈Cl₄Cr₄O₄Si₄
• 分子量: 1211.52
• InChiKey: BQPJVQOJHKSUIL-UHFFFAOYSA-J

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

• 作为反应物：
  描述：

  4-甲基吡啶 、 [Cr(μ-Cl)(μ-OSi(t)Bu3)]4 以 neat (no solvent) 为溶剂， 生成 ((t)Bu₃SiO)2Cr(4-picoline)3
  参考文献：
  名称：

  Low-Coordinate Chromium Siloxides:  The “Box” [Cr(μ-Cl)(μ-OSi^tBu₃)]₄, Distorted Trigonal [(^tBu₃SiO)₃Cr][Na(benzene)] and [(^tBu₃SiO)₃Cr][Na(dibenzo-18-c-6)], and Trigonal (^tBu₃SiO)₃Cr

  摘要：

  Treatment of CrCl2(THF)(2) with (NaOSiBu3)-Bu-t afforded the tetrameric '' box '' [Cr(u-Cl)(u-(OSiBu3)-Bu-t)](4) (1, X-ray). THF cleaved 1 to provide trans-(silox)ClCr(THF)(2) (2), whereas degradation of 1 with 4-picoline caused disproportionation and the generation of trans-Cl2Cr(4-pic)(2) and trans-(silcox)(2)Cr(4-pic)(x) (n = 2, 3; 3, 3-4-pic). Chromous centers in 1 were antiferromagnetically coupled, and density functional calculations on the high-spin (multiplicity = 17) model [Cr(mu-Cl)(mu-OH)](4) (1') revealed that its singly occupied 3d orbitals spanned an energy range of similar to 2 eV. The addition of 8 equiv of Na(silox) to 1 yielded [((Bu3SiO)-Bu-t)Cr(u-(OSiBu3)-Bu-t)2](NaC6H6)-C-. (4, Y shaped, < OCrO(Na) = 91.28(7)degrees), and treatment of 4 with dibenzo-18-crown-6 produced [(Silox)(3)Cr][Na(dibenzo-18-crown-6)] (5, < OCrO = similar to 120 degrees, (120 + alpha)degrees, (120 - alpha)degrees). Calculations of [((Bu3SiO)-Bu-t)Cr(mu-(OSiBu3)-Bu-t)(2)]Na (4') and Cr(silox)(3)(-) (5') provided reasonable matches with the experimental geometries (X-ray). The trigonal chromic derivative (silox)(3)Cr (6) was synthesized from CrCl3(THF)(3) for structural and calculational comparisons to the chromous derivatives.

  DOI：

  10.1021/ic0488334
• 作为产物：
  描述：

  trans-((t)Bu₃SiO)CrCl(tetrahydrofuran)2 以 苯 为溶剂， 生成 [Cr(μ-Cl)(μ-OSi(t)Bu3)]4
  参考文献：
  名称：

  Low-Coordinate Chromium Siloxides:  The “Box” [Cr(μ-Cl)(μ-OSi^tBu₃)]₄, Distorted Trigonal [(^tBu₃SiO)₃Cr][Na(benzene)] and [(^tBu₃SiO)₃Cr][Na(dibenzo-18-c-6)], and Trigonal (^tBu₃SiO)₃Cr

  摘要：

  Treatment of CrCl2(THF)(2) with (NaOSiBu3)-Bu-t afforded the tetrameric '' box '' [Cr(u-Cl)(u-(OSiBu3)-Bu-t)](4) (1, X-ray). THF cleaved 1 to provide trans-(silox)ClCr(THF)(2) (2), whereas degradation of 1 with 4-picoline caused disproportionation and the generation of trans-Cl2Cr(4-pic)(2) and trans-(silcox)(2)Cr(4-pic)(x) (n = 2, 3; 3, 3-4-pic). Chromous centers in 1 were antiferromagnetically coupled, and density functional calculations on the high-spin (multiplicity = 17) model [Cr(mu-Cl)(mu-OH)](4) (1') revealed that its singly occupied 3d orbitals spanned an energy range of similar to 2 eV. The addition of 8 equiv of Na(silox) to 1 yielded [((Bu3SiO)-Bu-t)Cr(u-(OSiBu3)-Bu-t)2](NaC6H6)-C-. (4, Y shaped, < OCrO(Na) = 91.28(7)degrees), and treatment of 4 with dibenzo-18-crown-6 produced [(Silox)(3)Cr][Na(dibenzo-18-crown-6)] (5, < OCrO = similar to 120 degrees, (120 + alpha)degrees, (120 - alpha)degrees). Calculations of [((Bu3SiO)-Bu-t)Cr(mu-(OSiBu3)-Bu-t)(2)]Na (4') and Cr(silox)(3)(-) (5') provided reasonable matches with the experimental geometries (X-ray). The trigonal chromic derivative (silox)(3)Cr (6) was synthesized from CrCl3(THF)(3) for structural and calculational comparisons to the chromous derivatives.

  DOI：

  10.1021/ic0488334