[η⁵-1,2,4-(Me₃C)₃C₅H₂]2Th(NH-p-tolyl)₂ | 1323150-22-6

• 英文名称: [η⁵-1,2,4-(Me₃C)₃C₅H₂]2Th(NH-p-tolyl)₂
• 英文别名: [η5-1,2,4-(Me3C)3C5H2]2Th(NH-p-tolyl)2
• CAS: 1323150-22-6
• 化学式: C₄₈H₇₄N₂Th
• 分子量: 911.167
• InChiKey: RBTQALXCQYYIED-UHFFFAOYSA-N

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：

  [η⁵-1,2,4-(Me₃C)₃C₅H₂]2Th(NH-p-tolyl)₂ 140.0 ℃ 、1.33 Pa 条件下， 生成 [η⁵-1,2,4-(Me3C)3C5H2]2Th=N(p-tolyl)
  参考文献：
  名称：

  Small Molecule Activation Mediated by a Thorium Terminal Imido Metallocene

  摘要：

  The base-free thorium terminal imido [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th=N(p-tolyl) (1) activates a variety of small molecules such as pyridine derivatives, amines, boranes, chlorosilane, elemental selenium, and alpha,beta-unsaturated esters. Reaction of 1 with pyridine, pyridine N-oxide, 2-methylpyridine N-oxide, p-toluidine, Ph2NH, 9-borabicyclo[3.3.1]nonane (9-BBN), PhSiH2Cl, elemental selenium, PhSeSePh, and methyl methacrylate (MMA) formed the amido pyridyl complexes [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(eta(2)-C,N-C5H4N) (2), [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(eta(2)-C,O-C5H4NO) (3), and [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(eta(2)-C,O-2-MeC5H3NO) (4), diamide complexes [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(2) (5) and [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(NPh2) (6), amido hydrido complex [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(H)[N(p-tolyl)B(C8H14)] (7), amido chloride complex [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(Cl)[N(p-tolyl)SiH2Ph] (8), amido selenido complexes [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th[N(p-tolyl)SeSe] (9) and {[eta(5)-1,2,4-(Me3C)(3)C5H2]Th(SePh)}(2)[mu-N(p-tolyl)](2) (10), and amido enolyl complex [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th[N(p-tolyl)CH2C(Me)=C(OMe)O] (11). The new complexes 2-3 and 6-11 were characterized by various spectroscopic techniques including single crystal X-ray diffraction. Furthermore, density functional theory (DFT) studies complement the experimental investigations.

  DOI：

  10.1021/acs.organomet.5b00454
• 作为产物：
  描述：

  [η⁵-1,2,4-(Me₃C)₃C₅H₂]₂Th(NH-p-tolyl)(NPh₂) 、 乙烷,三氯氟- 以 氘代苯 为溶剂， 反应 24.0h， 生成 [η⁵-1,2,4-(Me₃C)₃C₅H₂]2Th(NH-p-tolyl)₂
  参考文献：
  名称：

  Small Molecule Activation Mediated by a Thorium Terminal Imido Metallocene

  摘要：

  The base-free thorium terminal imido [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th=N(p-tolyl) (1) activates a variety of small molecules such as pyridine derivatives, amines, boranes, chlorosilane, elemental selenium, and alpha,beta-unsaturated esters. Reaction of 1 with pyridine, pyridine N-oxide, 2-methylpyridine N-oxide, p-toluidine, Ph2NH, 9-borabicyclo[3.3.1]nonane (9-BBN), PhSiH2Cl, elemental selenium, PhSeSePh, and methyl methacrylate (MMA) formed the amido pyridyl complexes [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(eta(2)-C,N-C5H4N) (2), [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(eta(2)-C,O-C5H4NO) (3), and [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(eta(2)-C,O-2-MeC5H3NO) (4), diamide complexes [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(2) (5) and [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(NPh2) (6), amido hydrido complex [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(H)[N(p-tolyl)B(C8H14)] (7), amido chloride complex [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(Cl)[N(p-tolyl)SiH2Ph] (8), amido selenido complexes [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th[N(p-tolyl)SeSe] (9) and {[eta(5)-1,2,4-(Me3C)(3)C5H2]Th(SePh)}(2)[mu-N(p-tolyl)](2) (10), and amido enolyl complex [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th[N(p-tolyl)CH2C(Me)=C(OMe)O] (11). The new complexes 2-3 and 6-11 were characterized by various spectroscopic techniques including single crystal X-ray diffraction. Furthermore, density functional theory (DFT) studies complement the experimental investigations.

  DOI：

  10.1021/acs.organomet.5b00454

文献信息

• Thorium Oxo and Sulfido Metallocenes: Synthesis, Structure, Reactivity, and Computational Studies
  作者：Wenshan Ren、Guofu Zi、De-Cai Fang、Marc D. Walter

  DOI：10.1021/ja205280k

  日期：2011.8.24

  4-(Me(3)C)(3)C(5)H(2)](2)Th═N(p-tolyl) (4), which is a useful precursor for the preparation of oxo and sulfido thorium metallocenes [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)Th═E (E = O (5) and S (15)) by cycloaddition-elimination reaction with Ph(2)C═E (E = O, S) or CS(2). The oxo metallocene 5 acts as a nucleophile toward alkylsilyl halides, while sulfido metallocene 15 does not. The oxo metallocene 5 and sulfido

  已经全面研究了氧化钍和硫化金属茂的合成、结构和反应性。加热二甲基茂金属 [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)ThMe(2) (2) 的等摩尔混合物和双酰胺茂金属 [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)Th(NH-p-tolyl)(2 ) (3) 在回流甲苯中产生无碱的亚氨基钍茂金属，[η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2 )Th=N(p-tolyl) (4)，它是制备氧代和硫化钍金属茂的有用前体 [η(5)-1,2,4-(Me(3)C)(3)C (5)H(2)](2)Th=E (E = O (5) 和 S (15)) 通过与 Ph(2)C=E (E = O, S) 或 CS( 2）。氧代金属茂 5 充当对烷基甲硅烷基卤化物的亲核试剂，而硫代金属茂 15 则不然。羰基茂金属 5 和硫化茂金属 15