(C5H5BPh)(η5-C5Me5)ZrCl2 | 210573-38-9

• 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)(η5-C5Me5)ZrCl2
• 英文别名: dichlorozirconium(2+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene;1-phenyl-1-boranuidacyclohexa-1,3,5-triene
• CAS: 210573-38-9
• 化学式: C₂₁H₂₅BCl₂Zr
• 分子量: 450.37
• InChiKey: JEZSIAKRNKXYSG-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.03
• 重原子数：
  25
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 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)(η5-C5Me5)ZrCl2 、 一氧化碳 在 Mg 作用下， 以 四氢呋喃 为溶剂， 生成 (C5H5BPh)(η5-C5Me5)Zr(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：

  pentamethylcyclopentadienylzirconium(IV) trichloride 、 以 乙醚 为溶剂， 以85%的产率得到(C5H5BPh)(η5-C5Me5)ZrCl2
  参考文献：
  名称：

  9-Phenyl-9-borataanthracene 的锆配合物。合成、结构表征和反应性

  摘要：

  9-苯基-9-硼酸锂 (3·Li(THF)x, x = 2 或 3) 是由 9-苯基-9,10-二氢-9-硼酸锂 (6) 与 LiTMP (TMP) 脱质子化得到的= 2,2,6,6-四甲基哌啶）在 THF 中。6 和 3·Li(TMEDA)（TMEDA = N,N,N',N'-四甲基乙二胺）的晶体学确定结构的比较突出了电荷和离域对杂环骨架的影响。3·Li(THF)2 与 Cp*ZrCl3 (Cp* = C5Me5) 和 Cp*ZrMe2Cl 反应得到新型配合物 (AnB-Ph)Cp*ZrCl2 (4) (AnB-Ph = 9-phenyl-9-硼烷蒽) 和 (AnB-Ph)Cp*ZrMe2 (5)，分别。4 的晶体学确定的分子结构类似于弯曲的茂金属，配体在锆周围呈四面体排列。硼烷蒽配体显着弯曲（约 16°）以避免与 Cp*ZrCl2 核的空间接触。对于 6, 3·Li(TMEDA)，环外苯基取代基相对于蒽单元的角度在

  DOI：

  10.1021/ja972651+