tert-butyl-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl]azanide;N-tert-butylethanimine;zirconium(4+) | 193201-18-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: tert-butyl-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl]azanide;N-tert-butylethanimine;zirconium(4+)
• CAS: 193201-18-2
• 化学式: C₂₇H₅₁N₃SiZr
• 分子量: 537.032
• InChiKey: VMENUZYNIGCRHQ-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：

  tert-butyl-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl]azanide;N-tert-butylethanimine;zirconium(4+) 以 甲苯 为溶剂， 生成 tert-butyl-[(Z)-3-tert-butylazanidylbut-2-en-2-yl]azanide;tert-butyl-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl]azanide;zirconium(4+)
  参考文献：
  名称：

  Double Isocyanide Insertion and C,C-Coupling Reaction of [(C₅Me₄)SiMe₂(N-t-Bu)]ZrMe₂. Structural Characterization of the Two 1,4-Diaza-5-zirconacyclopentene Ring Conformations for [(C₅Me₄)SiMe₂(N-t-Bu)]Zr[N(R)C(Me)C(Me)N(R)] Complexes

  摘要：

  The reactions of 2 equiv of CNR (R = (a) tert-butyl, (b) 2,6-xylyl, (c) Me) with [(C5Me4)SiMe2(N-t-Bu)]ZrMe2, 1, proceed sequentially with isocyanide insertion into both Zr-C(methyl) bands of this 14-electron complex to give the corresponding eta(2)-iminoacyl Zr complexes [(C5Me4)SiMe2(N-t-Bu)]ZrMe[eta(2)-C(Me)NR], 2, and [(C5Me4)SiMe2(N-t-Bu)]Zr[eta(2)-C(Me)NR](2), 3. Subsequent thermolysis of 3 leads to C,C-coupling of the two eta(2)-iminoacyl units and proceeds solely with formation of the enediamidate derivative [(C5Me4)SiMe2(N- t-Bu)Zr[N(R)C(Me)=C(Me)N(R)], 4. Compounds 2a, 3a-c, and 4a-c have been observed and characterized by solution NMR measurements, and the molecular structures of 3a, 3b, 4a, and 4b have been confirmed by crystallographic methods, The nonplanar 1,4-diaza-5-zirconacyclopentene rings of 4a and 4b are folded by ca. 50 degrees in opposite directions along the corresponding N ... N line segment and adopt the prone and supine conformations, respectively. The activation parameters for the first-order intramolecular C,C-coupling reaction leading to the conversion of 3a --> 4a are Delta H double dagger = 24.6(2) kcal/mol and Delta S double dagger = -11.3(7) eu and of 3b --> 4b are Delta H double dagger = 23.9(3) kcal/mol and Delta S double dagger = -10.4(8) eu.

  DOI：

  10.1021/om9610760
• 作为产物：
  描述：

  [(η(5)-C5Me4)SiMe2(N-t-Bu)]ZrMe2 、 异氰酸叔丁酯 以 正戊烷 为溶剂， 以91%的产率得到tert-butyl-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl]azanide;N-tert-butylethanimine;zirconium(4+)
  参考文献：
  名称：

  Double Isocyanide Insertion and C,C-Coupling Reaction of [(C₅Me₄)SiMe₂(N-t-Bu)]ZrMe₂. Structural Characterization of the Two 1,4-Diaza-5-zirconacyclopentene Ring Conformations for [(C₅Me₄)SiMe₂(N-t-Bu)]Zr[N(R)C(Me)C(Me)N(R)] Complexes

  摘要：

  The reactions of 2 equiv of CNR (R = (a) tert-butyl, (b) 2,6-xylyl, (c) Me) with [(C5Me4)SiMe2(N-t-Bu)]ZrMe2, 1, proceed sequentially with isocyanide insertion into both Zr-C(methyl) bands of this 14-electron complex to give the corresponding eta(2)-iminoacyl Zr complexes [(C5Me4)SiMe2(N-t-Bu)]ZrMe[eta(2)-C(Me)NR], 2, and [(C5Me4)SiMe2(N-t-Bu)]Zr[eta(2)-C(Me)NR](2), 3. Subsequent thermolysis of 3 leads to C,C-coupling of the two eta(2)-iminoacyl units and proceeds solely with formation of the enediamidate derivative [(C5Me4)SiMe2(N- t-Bu)Zr[N(R)C(Me)=C(Me)N(R)], 4. Compounds 2a, 3a-c, and 4a-c have been observed and characterized by solution NMR measurements, and the molecular structures of 3a, 3b, 4a, and 4b have been confirmed by crystallographic methods, The nonplanar 1,4-diaza-5-zirconacyclopentene rings of 4a and 4b are folded by ca. 50 degrees in opposite directions along the corresponding N ... N line segment and adopt the prone and supine conformations, respectively. The activation parameters for the first-order intramolecular C,C-coupling reaction leading to the conversion of 3a --> 4a are Delta H double dagger = 24.6(2) kcal/mol and Delta S double dagger = -11.3(7) eu and of 3b --> 4b are Delta H double dagger = 23.9(3) kcal/mol and Delta S double dagger = -10.4(8) eu.

  DOI：

  10.1021/om9610760