Cp₂Zr[η⁴-^tBuC₄(^tBu)-C(C₂SiMe₃)=CSiMe₃] | 1549922-26-0

• 英文名称: Cp₂Zr[η⁴-^tBuC₄(^tBu)-C(C₂SiMe₃)=CSiMe₃]
• CAS: 1549922-26-0
• 化学式: C₃₂H₄₆Si₂Zr
• 分子量: 578.112
• InChiKey: BAOBNKMVMNCSKB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  在 2,2,7,7-四甲基-3,5-辛二炔 作用下， 以 甲苯 为溶剂， 反应 168.0h， 以0.280 g的产率得到Cp₂Zr[η⁴-^tBuC₄(^tBu)-C(C₂SiMe₃)=CSiMe₃]
  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

文献信息

• Thermal Isomerization of the Buchwald Seven-Membered Zirconacyclocumulene and Its Interaction with Acetylenes. Synthesis and Structures of Novel Seven-Membered Zirconacyclocumulene Complexes
  作者：Vladimir V. Burlakov、Vyacheslav S. Bogdanov、Perdita Arndt、Wolfgang Baumann、Anke Spannenberg、Konstantin A. Lyssenko、Ivan V. Ananyev、Uwe Rosenthal、Vladimir B. Shur

  DOI：10.1021/om501205s

  日期：2015.6.8

  On prolonged heating of the Buchwald seven-membered zirconacydocumulene Cp2Zr[eta(4)-Me3SiC4(SiMe3) C(C2SiMe3)=CSiMe3] (1) in toluene at 100 degrees C, the isomerization of 1 takes place with the formation of a seven-membered zirconacydocumulene complex, Cp2Zr[eta(4-)-Me3SiC4(SiMe3)-C(SiMe3)=C(C2SiMe3)] (8), containing the Me3SiC C group in a-position and the SiMe3 group in beta-position with respect to the Zr atom. A remarkable peculiarity of complex 8 is its ability to undergo a rapid degenerate rearrangement at room temperature in toluene solution, as a result of which only two rather than four singlets of the Me3Si groups are observed in the H-1 NMR spectrum of 8 under such conditions. At temperatures below 200 K, the rate of this rearrangement decreases and, as a consequence, the H-1 NMR spectrum of 8 acquires the normal view. If 1 is heated at 100 degrees C in the presence of acetylenes such as 1,4-bis(tert-butyl)butadiyne ((BuC)-Bu-t C-C (CBu)-Bu-t) and tolane, the corresponding seven-membered zirconacyclocumulenes, viz., Cp2Zr[eta(4)-(BuC4)-Bu-t(Bu-t)-C(C2SiMe3)=CSiMe3] (7) and Cp2Zr[eta(4)-Me3SiC4(SiMe3)-C(Ph)=CPh] (14), are formed along with free Me3SiC C-C CSiMe3. The interaction of 1 with 1,4-diphenylbutadiyne (PhC C-C CPh) at 100 degrees C leads to the formation of a mixture of products, from which a zirconacyclopentadiene metallacycle, Cp2Zr[eta(2)-PhC=C(C2Ph)-C(C2Ph)-CPh] (10), as well as seven-membered zirconacyclocumulenes Cp2Zr[eta(4)-PhC4(Ph)-C(C2SiMe3)=CSiMe3] (11), Cp2Zr[eta(4)-Me3SiC4(SiMe3)-C(C2Ph)=CPh] (12), and Cp2Zr[eta(4)-PhC4(Ph)-C(C2Ph)=CPh] (13) were isolated. The structures of 8, 9, 10, 12, and 14 have been established by X-ray crystallography. The mechanism of the reactions found is discussed.