(C5H5BPh)2ZrCl2 | 188130-16-7

• 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: (C5H5BPh)2ZrCl2
• 英文别名: bis(1-phenylboratabenzene)zirconium dichloride；Dichlorozirconium(2+);1-phenyl-1-boranuidacyclohexa-1,3,5-triene
• CAS: 188130-16-7
• 化学式: C₂₂H₂₀B₂Cl₂Zr
• 分子量: 468.153
• InChiKey: JOCIEXYTZAWUKF-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.78
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (C5H5BPh)2ZrCl2 、 一氧化碳 在 Mg 作用下， 以 四氢呋喃 为溶剂， 以31%的产率得到(C5H5BPh)2Zr(CO)2
  参考文献：
  名称：

  Electron-Donating Properties of Boratabenzene Ligands

  摘要：

  The reaction of (C5H5B-R)Cp*ZrMe2 (Cp* = eta(5)-C5Me5; R = NMe2 (4), OEt (5), Ph (6)) with B(C6F5)(3) affords zwitterionic complexes of the type [(C5H5B-R)Cp*ZrMe] [MeB(C6F5)(3)] (R = NMe2 (7), OEt (8), Ph (9)). The molecular structures of 7 and 9 were determined by single-crystal X-ray diffraction studies, and they were found to be similar to those observed for standard group 4 metallocenes. The boratabenzene ligand in 7 more closely resembles an eta(5)-pentadienyl fragment than in 9, where it is eta(6)-bound. Variable-temperature H-1 NMR spectroscopy shows that ion-pair dissociation/recombination processes occur in solution. Data over large temperature ranges were obtained by the combination of line shape and spin saturation transfer techniques (100 degrees C for 4 and 5, 65 degrees C for 4). The rates of these processes give insight into how the orbital overlap between boron and the exocyclic group affects the rates of elementary reactions at the metal. The Delta H-double dagger values for ion-pair dissociation/recombination were found to increase with decreasing donor strength of the substituent: 12.2(2), 12.6(1), and 17.6(3) kcal/mol for 7, 8, and 9, respectively. Exchange reactions between 9 and 4 reveal that 7 is formed exclusively, indicating that the aminoboratabenzene ligand can better accommodate the increased positive charge on the metal center. The dependence of the carbonyl stretching frequency on the extent of metal back-bonding in complexes of the type (C5H5B-R)Cp*Zr(CO)(2) (R = NMe2 (10), OEt (11), Me (12), Ph (13)) and (C5H5B-R)(2)Zr(CO)(2) (R = NMe2 (14), OEt (15), Me (16), Ph (17)) can also be used to gauge the electron density at Zr. Complexes 10-17 were prepared by reductive carbonylation of the corresponding dichlorides. The measured reduction potentials of the dichlorides, (C5H5B-R)(2)ZrCl2, show that it is progressively more difficult to reduce the metal center as the donor strength of the boratabenzene ligand increases. The dynamic NMR, IR, and electrochemical data are consistent with the notion that the donor properties in [C5H5B-R] ligands decrease in the order R = NMe2 > OEt approximate to Me > Ph.

  DOI：

  10.1021/ja992413+
• 作为产物：
  描述：

  氯化锆(IV) 、 1-phenyl-1,4-dihydroborabenzene 在 LDA 作用下， 以 乙醚 为溶剂， 以80%的产率得到(C5H5BPh)2ZrCl2
  参考文献：
  名称：

  （苯硼酸苯）锆配合物：调整烯烃聚合催化剂的反应性

  摘要：

  2当量的1-苯基硼硼酸锂与ZrCl 4在乙醚中的反应生成双（1-苯基硼硼苯）二氯化锆（2），而[4-叔-C 4 H 9 C 5 H 4 BPh] 2 ZrCl 2（3）对以类似方式获得的α，进行单晶X射线衍射研究。2和甲基铝氧烷（MAO）的溶液与C 2 H 4（1 atm，25°C）的反应产生乙烯低聚物（以1-烯烃为主要产物的二聚物，以及少量的1-和2-烯烃） ）。

  DOI：

  10.1021/om970103z

文献信息

• Boratabenzene Zirconium(II) Complexes: An Unusual Annulation with Ethynes
  作者：Arthur J. Ashe、Saleem Al-Ahmad、Jeff W. Kampf

  DOI：10.1002/anie.199720141

  日期：1997.10.2