Sc(CH2SiMe3)3(fac-κ3-1,4,7-trithiacyclononane) | 862891-13-2

• 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: Sc(CH2SiMe3)3(fac-κ3-1,4,7-trithiacyclononane)
• 英文别名: [Sc(1,4,7-trithiacyclononane)(CH2Si(CH3)3)3]；[Sc([9]aneS3)(CH2SiMe3)3]；Sc(CH2SiMe3)3([9]aneS3)；Methanidyl(trimethyl)silane;scandium(3+);1,4,7-trithionane
• CAS: 862891-13-2
• 化学式: C₁₈H₄₅S₃ScSi₃
• 分子量: 486.966
• InChiKey: ZHKIGTLPUXNMNZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.29
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  75.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Sc(CH2SiMe3)3(fac-κ3-1,4,7-trithiacyclononane) 以 四氢呋喃 为溶剂， 生成 [Sc(CH2SiMe3)2(THF)(fac-tris(3,5-dimethylpyrazolyl)methane)](BPh4)
  参考文献：
  名称：

  Synthesis, DFT Studies, and Reactions of Scandium and Yttrium Dialkyl Cations Containing Neutral fac-N₃ and fac-S₃ Donor Ligands

  摘要：

  Reaction of Sc(CH2SiMe3)(3)(THF)(2) with 1,4,7-trithiacyclononane gave Sc([9]aneS(3))(CH2SiMe3)(3), the first organometallic group 3 complex of [9]aneS(3) ([9]aneS(3) = 1,4,7-trithiacyclononane). The corresponding reaction for yttrium gave equilibrium mixtures of Y([9]aneS(3))(CH2SiMe3)(3) and starting materials. Density functional theory (DFT) was used to compare the energies of formation and metal-ligand interaction energies for M([9]aneS(3))R-3 with those for the previously reported fac-N-3 donor complexes M(fac-N-3)R-3 (R = Me or CH2SiMe3; fac-N-3 = 1,4,7-trimethyltriazacyclononane (Me-3[9]aneN(3)) or HC(Me(2)pz)(3)). Reaction of M(CH2SiMe3)(3)(THF)(2) with [NHMe2Ph][BAr4F] (Ar-F = C6F5) in the presence of a facecapping ligand L (L = HC(Me(2)pz)(3), Me-3[9]aneN(3), or [9]aneS(3)) gave the cationic complexes [M(L)(CH2SiMe3)2(THF)](+), which has been structurally characterized for M = Sc and L = [9]aneS3. The corresponding base-free cations [M(L)(CH2SiMe3)(2)](+) were studied by Si-29 NMR spectroscopy and/or DFT and found to possess beta-Si-C agostic alkyl groups in most instances. The isolated cations [Sc(fac-N-3)(CH2SiMe3)(2)(THF)](+) underwent THF substitution reactions with OPPh3 or pyridine, Sc-alkyl migratory insertion with carbodiimides, and C-H bond metathesis with PhCCH. The olefin polymerization capabilities of a series of complexes M(L)R3 have been determined. The scandium complexes were found to be very productive for ethylene polymerization for L (L = HC(Me(2)pz)(3), Me-3[9]aneN(3), or [9]aneS(3) and R = CH2SiMe3 when activated with 1 equiv of [CPh3][BAr4F]. When activated with 2 equiv of [CPh3][BAr4F], the compounds were also very active for the polymerization of 1-hexene.

  DOI：

  10.1021/om800279d
• 作为产物：
  描述：

  1,4,7-三硫环壬烷 、 [scandium tris(trimethylsilylmethyl)(THF)2] 以 甲苯 为溶剂， 以75%的产率得到Sc(CH2SiMe3)3(fac-κ3-1,4,7-trithiacyclononane)
  参考文献：
  名称：

  The first rare earth organometallic complex of 1,4,7-trithiacyclononane: a precursor to unique cationic ethylene and α-olefin polymerisation catalysts supported by an all-sulfur donor ligand

  摘要：

  [Sc([9]aneS3)(CH2SiMe3)3]是 1,4,7-三硫杂环烷的首个稀土有机金属复合物，在与 BArF3 或 [CPh3][BArF4]（ArF = C6F5）活化后是乙烯和 α- 烯烃聚合催化剂的前体；这是首个由全硫供体配体支持的阳离子稀土有机金属催化剂。

  DOI：

  10.1039/b503967c