pentakis(4-n-butylphenyl)cyclopentadiene | 161296-28-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: pentakis(4-n-butylphenyl)cyclopentadiene
• 英文别名: Cp(BIG)H；YZ6Ahm38KB；1-butyl-4-[2,3,4,5-tetrakis(4-butylphenyl)cyclopenta-1,4-dien-1-yl]benzene
• CAS: 161296-28-2
• 化学式: C₅₅H₆₆
• 分子量: 727.129
• InChiKey: CZMWDGMAEHAEDB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17.4
• 重原子数：
  55
• 可旋转键数：
  20
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  pentakis(4-n-butylphenyl)cyclopentadiene 在 双(三甲基硅烷基)氨基钾 作用下， 以 乙腈 为溶剂， 反应 1.0h， 以91%的产率得到
  参考文献：
  名称：

  含有立体要求的五芳基环戊二烯基取代基的s和p嵌段金属配合物的合成和结构

  摘要：

  具有空间需求的环戊二烯基Cp BIG i -Pr M（Cp BIG i- Pr = Cp（4 - i -Pr-Ph）5 ; M = Li 1，Na 2，K 3，Rb 4，Cs的碱金属盐的合成5），Cp BIG n- Bu M（Cp BIG n- Bu = Cp（4- n -Bu-Ph）5 ; M = Li 6，Na 7，K 8，Rb 9，Cs 10）和Cp BIG t-Bu M（Cp BIG t- Bu = Cp（4- t -Bu-Ph）5 ; M = Li 11，Na 12，K 13，Rb 14，Cs 15）及其包括IR和杂核（1 H ，13 C，7 Li，23 Na，87 Rb，133 Cs被报道。此外，固态结构5，10，11，和13通过单晶X-射线衍射确定，揭示在固体状态（无限一维链结构的形成5，10）或溶剂分离的离子对（11，13）。Cp BIG t- Bu K 13与ECl 3的

  DOI：

  10.1021/acs.organomet.9b00203
• 作为产物：
  描述：

  C5H(C6H4COCH2CH2CH3-p)5 在 氢氧化钾 、 一水合肼 作用下， 以 various solvent(s) 为溶剂， 反应 3.0h， 以61%的产率得到pentakis(4-n-butylphenyl)cyclopentadiene
  参考文献：
  名称：

  Schumann, Herbert; Lentz, Alexander, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1994, vol. 49, # 12, p. 1717 - 1724

  摘要：

  DOI：

文献信息

• Superbulky metallocene complexes of the heavier alkaline-earth metals strontium and barium
  作者：Lars Orzechowski、Dirk F.-J. Piesik、Christian Ruspic、Sjoerd Harder

  DOI：10.1039/b809872g

  日期：——

  Superbulky sandwich complexes with the cyclopentadienyl ligand (4-nBu-C6H4)5Cp (abbreviated here as CpBIG) have been prepared by reaction of CpBIGH with benzylic strontium or barium reagents. Both metallocenes have been structurally characterized by single crystal X-ray diffraction. Even for the larger metallocene (CpBIG)2Ba a highly symmetric sandwich complex with parallel Cp rings was isolated (Cpcenter–Ba = 2.667(1) Å). Both structures show evidence for a C–H⋯C(π) network between the Cp ligands. These attractive forces induce an inward out-of-plane bending of the aryl substituents (Sr 3.4(2)°; Ba 5.3(2)°). A linear correlation between this bending angle and metal size has been found.

  通过 CpBIGH 与苄基锶或钡试剂的反应，制备出了环戊二烯配体 (4-nBu-C6H4)5Cp 的超脆性夹心配合物（此处简称为 CpBIG）。这两种茂金属都通过单晶 X 射线衍射获得了结构特征。即使是较大的茂金属 (CpBIG)2Ba 也分离出了一个具有平行 Cp 环的高度对称的夹心复合物（Cpcenter-Ba = 2.667(1) Å）。两种结构都显示出 Cp 配体之间存在 C-H⋯C(π) 网络。这些吸引力导致芳基取代基平面外向内弯曲（锶 3.4(2)°；钡 5.3(2)°）。这种弯曲角度与金属尺寸之间存在线性关系。
• Metal Atom Dynamics in Superbulky Metallocenes: A Comparison of (Cp^BIG)₂Sn and (Cp^BIG)₂Eu
  作者：Sjoerd Harder、Dominik Naglav、Peter Schwerdtfeger、Israel Nowik、Rolfe H. Herber

  DOI：10.1021/ic4028546

  日期：2014.2.17

  (Cp2Sn)-Sn-BIG (Cp-BIG = (4-n-Bu-C6H4)(5)cyclopentadienyl), prepared by reaction of 2 equiv of (CpNa)-Na-BIG with SnCl2, crystallized isomorphous to other known metallocenes with this ligand (Ca, Sr, Ba, Sm, Eu, Yb). Similarly, it shows perfect linearity, C-H center dot center dot center dot C(pi) bonding between the Cp-BIG rings and out-of-plane bending of the aryl substituents toward the metal. Whereas all other (Cp2M)-M-BIG complexes show large disorder in the metal position, the Sn atom in (Cp2Sn)-Sn-BIG is perfectly ordered. In contrast, Sn-119 and Eu-151 Mossbauer investigations on the corresponding (Cp2M)-M-BIG metallocenes show that Sn(II) is more dynamic and loosely bound than Eu(II). The large displacement factors in the group 2 and especially in the lanthanide(II) metallocenes (Cp2M)-M-BIG can be explained by static metal disorder in a plane parallel to the Cp-BIG rings. Despite parallel Cp-BIG rings, these metallocenes have a nonlinear CDcenter-M-CPcenter geometry. This is explained by an ionic model in which metal atoms are polarized by the negatively charged Cp rings. The extent of nonlinearity is in line with trends found in M2+ ion polarizabilities. The range of known calculated dipole polarizabilities at the Douglas-Kroll CCSD(T) level was extended with values (atomic units) for Sn2+ 15.35, Sm2+(4f(67)F) 9.82, Eu2+(4f(7) S-8) 8.99, and Yb2+(4f(14) S-1)) 6.55. This polarizability model cannot be applied to predominantly covalently bound (Cp2Sn)-Sn-BIG, which shows a perfectly ordered structure. The bent geometry of Cp*Sn-2 should therefore not be explained by metal polarizability but is due to van der Waals Cp*center dot center dot center dot Cp* attraction and (to some extent) to a small p-character component in the Sn lone pair.

  (CP₂Sn)-Sn-BIG（CP-BIG = (4-n-Bu-C₆H₄)(5)-cyclopentadienyl），通过2当量的(CPNa)-Na-BIG与SnCl₂反应制备，其结晶结构与已知使用该配体的其他金属羰基物（Ca、Sr、Ba、Sm、Eu、Yb）同源。类似地，其表现出完美的线性结构，在CP-BIG环之间存在C-H·...·C(π)键合，以及芳基取代基相对于金属的平面外弯曲。然而，与其他所有(CP₂M)-M-BIG复合物相比，(CP₂Sn)-Sn-BIG中的Sn原子呈现出完美的有序性。相比之下，Sn-119和Eu-151穆斯堡尔研究表明，与Eu(II)相比，Sn(II)的动态行为更为活跃且结合较为松弛。在第2族和尤其在镧系(II)金属羰基物(CP₂M)-M-BIG中，较大的位移因子可以用与CP-BIG环平行的平面内金属无序状态来解释。尽管CP-BIG环是平行的，但这些金属羰基物具有非线性CD中心-M-CP中心几何结构。这可以通过一个离子模型来解释，其中金属原子被带负电的CP环极化。非线性的程度与M²+离子极化率的变化趋势一致。计算的二极矩极化率在Douglas-Kroll CCSD(T)水平下扩展到了已知范围，Sn²+为15.35，Sm²+（4f⁶⁷F）为9.82，Eu²+（4f⁷ S-8）为8.99，Yb²+（4f¹⁴ S-1）为6.55（原子单位）。然而，这一极化率模型不适用于主要是共价键合的(CP₂Sn)-Sn-BIG，因为该结构呈现出完全有序的特性。因此，CP*Sn-2的弯曲几何结构不应归因于金属极化，而是由于CP*·...·CP*的范德华吸引力（在某种程度上）以及Sn孤对中较小的p特性所致。
• Remarkable Stability of Metallocenes with Superbulky Ligands: Spontaneous Reduction of SmIII to SmII
  作者：Christian Ruspic、John R. Moss、Markus Schürmann、Sjoerd Harder

  DOI：10.1002/anie.200705001

  日期：2008.2.28
• Insight in cyclopentadienyl metal complexes with superbulky ligands: The crystal structure of [CpBIGK]∞
  作者：Sjoerd Harder、Christian Ruspic

  DOI：10.1016/j.jorganchem.2008.09.073

  日期：2009.4

  Reaction of (4-nBu-C6H4)(5)CpH (=(CpH)-H-BIG) with KH in THF and subsequent recrystallization from hexane/Et2O gave the solvent-free product (CpK)-K-BIG in good crystalline yield (55%). Crystal structure determination revealed the one-dimensional coordination polymer [(CpK)-K-BIG](infinity). Despite the steric bulk of the Cp-BIG ligands, the chains are not perfectly linear. They can be pictured as an array of highly symmetric (Cp-BIG)(2)K- sandwiches bridged by K+ ions at an angle of 167.7(2)degrees. The C-K bond distances are much shorter than those in other cyclopentadienyl potassium complexes. This is explained by networks of attractive C-H center dot center dot center dot C(pi) interactions between neighbouring CpBIG ligands. In all cases the C-H donors and C acceptors are represented by the ortho-CH units in the aryl substituents. The C-H center dot center dot center dot C(pi) networks within the supersandwich are less distinct than those observed in the metallocene sandwich complexes (Cp-BIG)(2)M (M = Ca, Sr, Ba, Yb, Sm). Significant out-of-plane bending of the aryl substituents indicates that, within the supersandwich chain, pairs of tighter C-H center dot center dot center dot C(pi) networks exist. Large displacement factors for the K+ ions are explained by assuming induced polarization of these soft metals. This results in enforcement of the Cp-BIG-K interactions. (C) 2008 Published by Elsevier B.V.