Cp2Zr[η2-tBuC=C(C2tBu)–C(Ph)=CPh] | 1549921-88-1

• 英文名称: Cp2Zr[η2-tBuC=C(C2tBu)–C(Ph)=CPh]
• 英文别名: Cp₂Zr[η²-^tBuC=C(C₂^tBu)-C(Ph)=CPh]
• CAS: 1549921-88-1
• 化学式: C₃₆H₃₈Zr
• 分子量: 561.922
• InChiKey: RXPQJBTZCJZPGX-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：

  Cp2Zr[η2-tBuC=C(C2tBu)–C(Ph)=CPh] 以 氘代甲苯 为溶剂， 反应 240.0h， 生成 1,1-bis(cyclopentadienyl)zircona-2,3,4,5-tetraphenylcyclopentadiene 、 2,2,7,7-四甲基-3,5-辛二炔 、 Cp₂Zr(η⁴-^tBuC₄^tBu)
  参考文献：
  名称：

  Interaction of the five-membered zirconacyclocumulene complex Cp2Zr(η4-tBuC4tBu) with acetylenes. Synthesis of zirconacyclopentadienes and seven-membered zirconacyclocumulenes

  摘要：

  In the interaction of the five-membered zirconacyclocumulene Cp2Zr(eta(4)-(BuC4Bu)-Bu-t-Bu-t) (6) with 1,4-bis(trimethylsilyl)butadiyne Me3SiC C-C CSiMe3 in toluene at 60-80 degrees C, two isomeric zirconacyclopentadiene complexes (7) and (8) are formed in 4.4-4.7 : 1 ratio. Complex 7 has been isolated from the solution in the individual state and its structure Cp2Zr[eta(2)-(BuC)-Bu-t=C(C-2 Bu-t)-C(SiMe3)=C(C2SiMe3)] has been determined by X-ray crystallography. Prolonged heating of a mixture of 6 and Me3SiC C-C CSiMe3 at 100 degrees C leads to a gradual disappearance of the resulting zirconacyclopentadienes and to the formation of the seven-membered zirconacyclocumulene complex Cp2Zr[eta(4)-(BuC4)-Bu-t(Bu-t)-C(C2SiMe3)]=CSiMe3] (9) as the main product and two its analogues, viz., Cp2Zr[eta(4)-Me3SiC4(SiMe3)-C(C2SiMe3)]=CSiMe3] (1) and Cp2Zr[eta(4)-(BuC4)-Bu-t(Bu-t)-C(C-2 Bu-t)=(CBu)-Bu-t] (2) as the admixtures. The same products are produced from individual compound 7 at 100 degrees C. Heating of complex 6 with tolane and phenylacetylene in toluene at 100 degrees C also gives rise to the corresponding zirconacyclopentadiene metallacycles, viz. Cp2Zr[eta(2)-(BuC)-Bu-t=C(C-2 Bu-t)-C(Ph)=CPh] (10) and Cp2Zr[eta(2)-(BuC)-Bu-t=C(C-2 Bu-t)-CH]=CPh] (11). However these metallacycles do not form seven-membered zirconacyclocumulene complexes in any significant amounts even under prolonged keeping of the mixture at 100 degrees C. The structure of complexes 9-11 has also been established by X-ray crystallography. Mechanisms of the reactions found are discussed. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.07.026
• 作为产物：
  描述：

  Cp₂Zr(η⁴-^tBuC₄^tBu) 、 二苯基乙炔 以 甲苯 为溶剂， 反应 72.0h， 以68%的产率得到Cp2Zr[η2-tBuC=C(C2tBu)–C(Ph)=CPh]
  参考文献：
  名称：

  Interaction of the five-membered zirconacyclocumulene complex Cp2Zr(η4-tBuC4tBu) with acetylenes. Synthesis of zirconacyclopentadienes and seven-membered zirconacyclocumulenes

  摘要：

  In the interaction of the five-membered zirconacyclocumulene Cp2Zr(eta(4)-(BuC4Bu)-Bu-t-Bu-t) (6) with 1,4-bis(trimethylsilyl)butadiyne Me3SiC C-C CSiMe3 in toluene at 60-80 degrees C, two isomeric zirconacyclopentadiene complexes (7) and (8) are formed in 4.4-4.7 : 1 ratio. Complex 7 has been isolated from the solution in the individual state and its structure Cp2Zr[eta(2)-(BuC)-Bu-t=C(C-2 Bu-t)-C(SiMe3)=C(C2SiMe3)] has been determined by X-ray crystallography. Prolonged heating of a mixture of 6 and Me3SiC C-C CSiMe3 at 100 degrees C leads to a gradual disappearance of the resulting zirconacyclopentadienes and to the formation of the seven-membered zirconacyclocumulene complex Cp2Zr[eta(4)-(BuC4)-Bu-t(Bu-t)-C(C2SiMe3)]=CSiMe3] (9) as the main product and two its analogues, viz., Cp2Zr[eta(4)-Me3SiC4(SiMe3)-C(C2SiMe3)]=CSiMe3] (1) and Cp2Zr[eta(4)-(BuC4)-Bu-t(Bu-t)-C(C-2 Bu-t)=(CBu)-Bu-t] (2) as the admixtures. The same products are produced from individual compound 7 at 100 degrees C. Heating of complex 6 with tolane and phenylacetylene in toluene at 100 degrees C also gives rise to the corresponding zirconacyclopentadiene metallacycles, viz. Cp2Zr[eta(2)-(BuC)-Bu-t=C(C-2 Bu-t)-C(Ph)=CPh] (10) and Cp2Zr[eta(2)-(BuC)-Bu-t=C(C-2 Bu-t)-CH]=CPh] (11). However these metallacycles do not form seven-membered zirconacyclocumulene complexes in any significant amounts even under prolonged keeping of the mixture at 100 degrees C. The structure of complexes 9-11 has also been established by X-ray crystallography. Mechanisms of the reactions found are discussed. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.07.026