2-[Bis(2-trimethylsilylazanidylethyl)amino]ethyl-trimethylsilylazanide;molybdenum(4+);trifluoromethanesulfonate | 197302-10-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 2-[Bis(2-trimethylsilylazanidylethyl)amino]ethyl-trimethylsilylazanide;molybdenum(4+);trifluoromethanesulfonate
• CAS: 197302-10-6
• 化学式: C₁₆H₃₉F₃MoN₄O₃SSi₃
• 分子量: 604.768
• InChiKey: HKUKUONHPDMQQW-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.96
• 重原子数：
  31
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  71.8
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  2-[bis(2-trimethylsilylazanidylethyl)amino]ethyl-trimethylsilylazanide;molecular nitrogen;molybdenum(3+) 以 氘代苯 为溶剂， 生成 2-[Bis(2-trimethylsilylazanidylethyl)amino]ethyl-trimethylsilylazanide;molybdenum(4+);trifluoromethanesulfonate
  参考文献：
  名称：

  Synthesis of [(Me₃SiNCH₂CH₂)₃N]^3- and [(C₆F₅NCH₂CH₂)₃N]^3- Complexes of Molybdenum and Tungsten That Contain CO, Isocyanides, or Ethylene

  摘要：

  Paramagnetic complexes of the type [N3N]MoL ([N3N](3-) = [(Me3SiNCH2CH2)(3)N](3-); L = CO, RNC, C2H4) have been prepared by displacing dinitrogen from [N3N]Mo(N-2). [N3N]Mo(CO) was reduced by magnesium powder in the presence of Me3SiCl to yield the diamagnetic oxycarbyne complex [N3N]Mo=COSiMe3, while oxidation of [N3N]Mo(CN-t-Bu) with [Cp2Fe]OTf yielded {[N3N]Mo(CN-t-Bu)}OTf. Thermolysis of [N3N]Mo(CN-t-Bu) resulted in loss of a t-Bu radical to yield [N3N]Mo(CN), which was structurally characterized, [N3NFML ([N3NF](3-) = [(C6F5NCH2CH2)(3)N](3-) M = Mo, W; L = CO, RNC) complexes have been prepared by one-electron reduction of [N3NF]M(OTf) in the presence of L. An X-ray study of [N3NF]W(CN-t-Bu) showed it to contain a bend isocyanide ligand. Anionic CO complexes were prepared by the two-electron reduction of [N3NF]M(OTf) in the presence of CO. An X-ray study of {[N3NF]W(CO)(2)}Na(ether)(3) revealed it to have a pseudo-octahedral structure in which sodium is bound to the CO trans tb the amine donor atom. Treatment of {[N3NF]M(CO)}(-) complexes with Me3SiCl gave oxycarbyne complexes [N3NF]M=COSiMe3. Reaction of [N3NF]WCO with V(Mes)(3)(THF) yielded [N3NF]W(CO)V(Mes)(3), the structure of which was determined in an X-ray study. Cationic [N3NF](3-) complexes could be prepared that contain up to 3 equiv of isocyanide. An X-ray study of {[N3NF]W(CN-t-Bu)(3)}BPh4 showed it to be a seven-coordinate species with one isocyanide located in the equatorial plane and the other two isocyanide ligands in the apical pocket. Reduction of [N3NF]W(OTf) under ethylene gave [N3NF]W(C2H4), which could be oxidized to yield diamagnetic {[N3NF]W(C2H4)}OTf.

  DOI：

  10.1021/om990748u

文献信息

• Synthesis and Decomposition of Alkyl Complexes of Molybdenum(IV) That Contain a [(Me₃SiNCH₂CH₂)₃N]^3- Ligand. Direct Detection of α-Elimination Processes That Are More than Six Orders of Magnitude Faster than β-Elimination Processes
  作者：Richard R. Schrock、Scott W. Seidel、Nadia C. Mösch-Zanetti、Keng-Yu Shih、Myra B. O'Donoghue、William M. Davis、William M. Reiff

  DOI：10.1021/ja970697x

  日期：1997.12.1

  behavior. The cyclopentyl and cyclohexyl complexes show another type of temperature-dependent fluxional behavior that can be ascribed to a rapid and reversible α-elimination process. For the cyclopentyl complex the rate constant for α-elimination is ∼103 s-1 at room temperature, while the rate co...

  多种顺磁性钼配合物，[N3N]MoR([N3N]3-=[(Me3SiNCH2CH2)3N]3-；R=Me、Et、Bu、CH2Ph、CH2SiMe3、CH2CMe3、环丙基、环丁基、环戊基、环己基、环戊烯基, 苯基), 由 [N3N]MoCl 制备。已检查的几个都遵循居里-魏斯 S = 1 行为，固态磁矩介于 2.4 和 2.9 μΒ 之间，低至 50 K。低于 50 K，有效磁矩急剧下降，这是由于提出是自旋轨道耦合和零场分裂效应的组合。由于主链“锁定”成一个 C3 对称构象和居里-魏斯行为的结果，NMR 谱依赖于温度。环戊基和环己基配合物显示出另一种类型的温度依赖性通量行为，可归因于快速且可逆的 α-消除过程。对于环戊基配合物，α-消除的速率常数在室温下为 ∼103 s-1，而速率常数...
• Triamidoamine Complexes of Molybdenum and Tungsten That Contain Metal−E (E = N, P, and As) Single, Double, or Triple Bonds
  作者：Nadia C. Mösch-Zanetti、Richard R. Schrock、William M. Davis、Klaus Wanninger、Scott W. Seidel、Myra B. O'Donoghue

  DOI：10.1021/ja971727z

  日期：1997.11.1

  Addition of two or more equivalents of LiPPhH to [N3N]MCl ([N3N]3- = [(Me3SiNCH2CH2)3N]3-; M = Mo or W) produced [N3N]M⋮P complexes via intermediate [N3N]M(PPhH) complexes. The reaction between [N3...

  将两个或更多等价的 LiPPhH 添加到 [N3N]MCl ([N3N]3- = [(Me3SiNCH2CH2)3N]3-; M = Mo 或 W) 中，通过中间体 [N3N]M( PPhH) 络合物。[N3 之间的反应...