[Cp2ZrCCMe)(C(Ph)C(CCPh)PPh2)] | 958635-66-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Cp2ZrCCMe)(C(Ph)C(CCPh)PPh2)]
• 英文别名: cyclopenta-1,3-diene;1,4-diphenylbut-1-en-3-yn-2-yl(diphenyl)phosphane;prop-1-yne;zirconium(4+)
• CAS: 958635-66-0
• 化学式: C₄₁H₃₃PZr
• 分子量: 647.911
• InChiKey: DRYNMVFFYWRTTC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.31
• 重原子数：
  43
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.02
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  [Cp2Zr(Cl)(C(Ph)C(CCPh)PPh2)] 、 丙基锂 以 四氢呋喃 、 甲苯 为溶剂， 以56%的产率得到[Cp2ZrCCMe)(C(Ph)C(CCPh)PPh2)]
  参考文献：
  名称：

  Formation and Structural and Dynamic Features of Atropisomeric η²-Iminoacyl Zirconium Complexes

  摘要：

  The Cp2ZrCl(mu-1,4-diphenylbutenyne)PX complexes 7a [-P(C6H5)2] and 10 [-P(C6F5)21 insert tertbutylisonitrile into the Zr-C(sp 2) cr bond to yield the N-inside 17 eta(2)-iminoacyl zirconocene complexes 13a and 13b. X-ray crystal structure analysis of complexes 13a and 13b revealed the presence of a chiral atropisomeric structure with a torsion angle of 74.8(2)degrees (13a) and 72.9(6)degrees (13b), respectively, around the central iminoacyl/alkenyl C(sp(2))-C(sp(2)) a bond. In solution an analogous chiral structure is observed. The barrier of interconversion of the enantiomeric atropisomers of 13a and 13b was determined at Delta G(double dagger) (327K) = 14.9 +/- 0.3 kcal mol(-1) (13a) and Delta G(double dagger) (325K) = 14.8 0.3 kcal mol(-1) (13b) by temperature-dependent dynamic NMR spectroscopy. Reaction of 7a and 10 with methyllithium followed by treatment with B(C6F5)3 gave the corresponding cationic zirconocene complexes 12a and 12b. These complexes took up 2 mol equiv of tert-butylisonitrile to yield the cationic N-inside eta(2)-iminoacyl zirconocene systems 14a and 14b as isonitrile adducts. The cationic complexes 14a and 14b are also axially chiral. The barriers of enantiomerization (Delta G(double dagger) (288 K) = 13.1 0 3 kcal mol(-1) (14a), Delta G(double dagger) (293 K) = 13.4 0.3 kcal mol(-1) (14b)) were also determined by dynamic NMR spectroscopy.

  DOI：

  10.1021/om7005968