Sc(CH2SiMe3)3(fac-tris(3,5-dimethylpyrazolyl)methane) | 658705-06-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: Sc(CH2SiMe3)3(fac-tris(3,5-dimethylpyrazolyl)methane)
• 英文别名: [(tris(3,5-dimethylpyrazolyl)methane)Sc(CH2SiMe3)3]；[Sc(HC(2,4-Me2pz)3)(CH2SiMe3)3]；Sc(CH2SiMe3)3(HC(Me2pz)3)；1-[Bis(3,5-dimethylpyrazol-1-yl)methyl]-3,5-dimethylpyrazole;methanidyl(trimethyl)silane;scandium(3+)
• CAS: 658705-06-7
• 化学式: C₂₈H₅₅N₆ScSi₃
• 分子量: 604.997
• InChiKey: JGLOJTVBCFZHEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.77
• 重原子数：
  38
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  53.5
• 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-tris(3,5-dimethylpyrazolyl)methane) 以 not given 为溶剂， 生成 [Sc(1,4,7-trithiacyclononane)(CH2Si(CH3)3)2(THF)][B(C6F5)4]
  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：

  Sc(CH2SiMe3)3(fac-1,4,7-trimethyl-1,4,7-triazacyclononane) 以 氘代苯 为溶剂， 生成 Sc(CH2SiMe3)3(fac-tris(3,5-dimethylpyrazolyl)methane)
  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

文献信息

• A Family of Scandium and Yttrium Tris((trimethylsilyl)methyl) Complexes with Neutral N₃ Donor Ligands
  作者：Cara S. Tredget、Sally C. Lawrence、Benjamin D. Ward、Robert G. Howe、Andrew R. Cowley、Philip Mountford

  DOI：10.1021/om050209r

  日期：2005.6.20

  HC(Me2pz)3, or Me3[6]aneN3 gave the corresponding tris((trimethylsilyl)methyl) derivatives M(Me3[9]aneN3)(CH2SiMe3)3 (M = Sc (1), Y (2)), MHC(Me2pz)3}(CH2SiMe3)3 (M = Sc (3), Y (4)), and M(Me3[6]aneN3)(CH2SiMe3)3 (M = Sc (12), Y (13)). Reaction of 3 with 2,6-dimethylphenol (ArOH) gave the tris(aryloxide) derivative ScHC(Me2pz)3}(OAr)3 (9), and reaction of HC(Me2pz)3 with MCl3 gave MHC(Me2pz)3}Cl3 (M

  报道了含有三（3,5-二甲基吡唑基）甲烷（HC（Me 2 pz）3）和1,3,5-三甲基三氮杂环己烷（Me 3 [6] aneN 3）配体的第一组3有机金属化合物，以及同源的1,4,7-三氮杂环壬烷负载的化合物和许多配体的三氯化物衍生物。M（CH 2 SiMe 3）3（THF）2（M = Sc，Y）与Me 3 [9] aneN 3（1,4,7-三甲基三氮杂环壬烷），HC（Me 2 pz）3或Me 3反应[6] aneN 3得到相应的三（（三甲基甲硅烷基）甲基）衍生物M（Me 3 [9] aneN 3）（CH 2 SiMe 3）3（M = Sc（1），Y（2）），M HC（Me 2 pz）3 }（CH 2 SiMe 3）3（M = Sc（3），Y（4））和M（Me 3 [6] aneN 3）（CH 2 SiMe 3）3（M = Sc（12），Y （13））。反应3与2,6-二甲基苯酚（ArOH）生成三（芳氧基）衍生物Sc
• Highly efficient ethylene polymerisation by scandium alkyls supported by neutral fac-κ³coordinated N₃donor ligands
  作者：Sally C. Lawrence、Benjamin D. Ward、Stuart R. Dubberley、Christopher M. Kozak、Philip Mountford

  DOI：10.1039/b310867h

  日期：——

  Reaction of [M(CH2SiMe3)3(THF)2] (M = Sc or Y) with the neutral fac-κ3 N3 donor ligands (L) Me3[9]aneN3 or HC(Me2pz)3 gave the corresponding trialkyls [M(L)(CH2SiMe3)3]; activation of the scandium congeners with B(C6F5)3 in the presence of ethylene afforded highly active polymerisation catalysts (Me3[9]aneN3 = 1,4,7-trimethyltriazacyclononane).

  [M(CH2SiMe3)3(THF)2]的反应 (M = Sc 或 Y) 与中性 fac-γ3 N3 供体配体 (L) Me3[9]aneN3 或 HC(Me2pz)3 得到相应的三烷基 [M(L)(CH2SiMe3)3]；在乙烯存在下用 B(C6F5)3 活化钪同系物可提供高活性聚合催化​​剂 (Me3[9]aneN3 = 1,4,7-三甲基三氮杂环壬烷）。