Cp(*)2Y(η(1)-CH2CH2CH2C(CH3)=CH2) | 204995-32-4

• 英文名称: Cp(*)2Y(η(1)-CH2CH2CH2C(CH3)=CH2)
• CAS: 204995-32-4；204995-31-3
• 化学式: C₂₆H₄₁Y
• 分子量: 442.517
• InChiKey: YRLPCXBFMIMVRP-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：
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• 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：

  2.5-二甲基四氢呋喃 、 Cp(*)2Y(η(1)-CH2CH2CH2C(CH3)=CH2) 以 further solvent(s) 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  d0Metal−Alkyl−烯烃配合物中烯烃络合的动力学和热力学

  摘要：

  来自钇螯合物 Cp*2Y[η1,η2-CH2CH2CH2CHCH2] (7-on) 的烯烃离解在 -100 °C 以下变得足够慢，可以通过动态 1H NMR 光谱[ΔG⧧(-110 °C) = 7.5 kcal mol -1，ΔH⧧ = 9.3 kcal mol-1]。Cp*2Y[η1,η2-CH2CH2CH(CH3)CHCH2] (8-on) 的 Cp* 共振的聚结需要烯烃解离加上钇的反转，并且发生速度明显慢于简单的烯烃解离 [ΔG⧧(-72 °C) = 9.6 kcal mol-1，ΔH⧧ = 10.8 kcal mol-1]。通过直接观察 Cp*2Y(η1,η2-CH2CH2CH2C(CH3)CH2) (6-on) 之间的平衡，确定双取代烯烃与 d0 钇中心的结合能为 ΔH° = 2.6 kcal mol-1和 Cp*2Y(η1-CH2CH2CH2C(CH3)CH2) (6-off)。与烯烃结合的

  DOI：

  10.1021/ja9931022
• 作为产物：
  描述：

  2-甲基-1,4-戊二烯 、 {(η5-C5Me5)2YH}2 以 氘代甲苯 为溶剂， 生成 Cp(*)2Y(η(1)-CH2CH2CH2C(CH3)=CH2)
  参考文献：
  名称：

  Coordination of a disubstituted alkene in a chelated d0-metal-alkyl-alkene complex. Evidence for equilibrium between complexes with coordinated and free alkenes

  摘要：

  Addition of (Cp-2*YH)(2)(4) to 2-methyl-1,4-pentadiene produced the yttrium-alkyl-alkene chelate complex Cp-2*YCH2CH2CH2C-(CH3)=CH2 (2) in which a disubstituted alkene is complexed to the metal center. Evidence for coordination of the alkene unit of 2 comes from the H-1 and C-13 NMR chemical shifts of the vinyl units and from observation of nOe effects between Cp* protons and vinyl hydrogens. The disubstituted alkene ligand of 2 is weakly bound, and evidence for an equilibrium with substantial amounts of complex 3 with a free alkene was obtained from variable temperature H-1 NMR spectroscopy. (C) 1998 Elsevier Science S.A.

  DOI：

  10.1016/s0020-1693(97)05852-0

文献信息

• Structural Dependence of Thermodynamics of Alkene Binding to Yttrium Alkyl Complexes and of Kinetics of Alkyl Migration to Coordinated Alkenes
  作者：Charles P. Casey、Jon A. Tunge、Ting-Yu Lee、Maureen A. Fagan

  DOI：10.1021/ja0209971

  日期：2003.3.1

  Agostic interactions in yttrium alkyls are structure dependent. Primary alkyl yttrium complexes have beta-CH2 agostic interactions at low temperature, but a shift toward alpha-agostic interactions occurs on warming. For the more crowded beta-disubstituted yttrium alkyls, an alpha-CH2 agostic interaction is seen. The thermodynamics of alkene binding to the primary alkyl yttrium complex CP*2YCH2CH2CH(CH3)(2) (2) depend strongly on the structure of the alkene. A single allylic substituent on the alkene has a small effect on alkene binding, but a second allylic substituent has a large destabilizing effect. Propene binding to yttrium alkyls is largely independent of the nature of the alkyl ligand. Equilibrium constants for propene binding to n-, gamma-substituted, beta-substituted, and secondary alkyl yttrium complexes are similar. The rate of migration of an alkyl group to a coordinated alkene depends strongly on the structure of the alkyl group: n-alkyl; gamma-substituted much greater than beta-substituted much greater than alpha-substituted. The similar to200-fold slower insertion of propene into Cp*2YCH(2)-CH(CH3)(2) (6) than that into CP*(2)gammaCH(2)CH(2)CH(CH3)(2) (2) is therefore due to kinetically slow migration of the beta-disubstituted alkyl group of 6 and not to differences in the equilibrium binding of propene. Processes related to chain transfer and site epimerization at the metal center are also reported.