(Me5C5)[C5H5BOEt]ZrCl2 | 220954-51-8

• 英文名称: (Me5C5)[C5H5BOEt]ZrCl2
• CAS: 220954-51-8
• 化学式: C₁₇H₂₅BCl₂OZr
• 分子量: 418.326
• InChiKey: MRMMVTZJHVVQRH-UHFFFAOYSA-L

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：

  trimethylaluminium dimer 、 (Me5C5)[C5H5BOEt]ZrCl2 以 not given 为溶剂， 生成 dichloro(1-methylboratabenzene)(pentamethylcyclopentadienyl)zirconium
  参考文献：
  名称：

  锆的烷氧基和芳氧基硼杂苯络合物

  摘要：

  将伯醇和仲醇添加到 C5H5B-PMe3 (2) 中以高产率提供 1-烷氧基硼环六-2,4-二烯。使用 NaH 或二异丙基氨基锂对这些硼环己二烯进行去质子化，然后与 ZrCl4 反应允许烷氧基硼杂苯配体与锆配位。因此，[C5H5B-OR]2ZrCl2 (R = Et, 1; Cy, 3; Ph, 4; and CH2Ph, 5) 类型的配合物可以以 45-65% 的总产率生产。4 的晶体学确定的分子结构显示了 B-O π 轨道重叠的证据。连接的二醇 1,2-反式-环己二醇和联萘酚可分别用于生成 ansa 型锆配合物 7 和 9。当 1、3、4 或 5 与 (AlMe3)2 反应时，有机金属产物是 [C5H5BMe]2ZrCl2 (10)。Cp*[C5H5B-OEt]ZrCl2 (11, Cp* = C5Me5) 和 (AlMe3)2 得到 Cp*[C5H5BMe]ZrCl2 (13)。

  DOI：

  10.1021/ja983270e
• 作为产物：
  描述：

  pentamethylcyclopentadienylzirconium(IV) trichloride 、 以 四氢呋喃 、 乙醚 为溶剂， 以77%的产率得到(Me5C5)[C5H5BOEt]ZrCl2
  参考文献：
  名称：

  锆的烷氧基和芳氧基硼杂苯络合物

  摘要：

  将伯醇和仲醇添加到 C5H5B-PMe3 (2) 中以高产率提供 1-烷氧基硼环六-2,4-二烯。使用 NaH 或二异丙基氨基锂对这些硼环己二烯进行去质子化，然后与 ZrCl4 反应允许烷氧基硼杂苯配体与锆配位。因此，[C5H5B-OR]2ZrCl2 (R = Et, 1; Cy, 3; Ph, 4; and CH2Ph, 5) 类型的配合物可以以 45-65% 的总产率生产。4 的晶体学确定的分子结构显示了 B-O π 轨道重叠的证据。连接的二醇 1,2-反式-环己二醇和联萘酚可分别用于生成 ansa 型锆配合物 7 和 9。当 1、3、4 或 5 与 (AlMe3)2 反应时，有机金属产物是 [C5H5BMe]2ZrCl2 (10)。Cp*[C5H5B-OEt]ZrCl2 (11, Cp* = C5Me5) 和 (AlMe3)2 得到 Cp*[C5H5BMe]ZrCl2 (13)。

  DOI：

  10.1021/ja983270e

文献信息

• Electron-Donating Properties of Boratabenzene Ligands
  作者：Guillermo C. Bazan、W. Donald Cotter、Zachary J. A. Komon、Rip A. Lee、Rene J. Lachicotte

  DOI：10.1021/ja992413+

  日期：2000.2.1

  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.