dichlorobis(1-methylboratabenzene)zirconium | 187328-52-5

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: dichlorobis(1-methylboratabenzene)zirconium
• 英文别名: (C5H5BMe)2ZrCl2；Dichlorozirconium(2+);1-methyl-1-boranuidacyclohexa-1,3,5-triene
• CAS: 187328-52-5
• 化学式: C₁₂H₁₆B₂Cl₂Zr
• 分子量: 344.011
• InChiKey: JLFUEWLYQCVWSC-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.88
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  dichlorobis(1-methylboratabenzene)zirconium 、 一氧化碳 在 Mg 作用下， 以 四氢呋喃 为溶剂， 生成 (C5H5BMe)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：

  1-methyl-2-(trimethylsilyl)-1,2-dihydroborinine 、 氯化锆(IV) 以 正己烷 为溶剂， 以95%的产率得到dichlorobis(1-methylboratabenzene)zirconium
  参考文献：
  名称：

  硼苯衍生物。26. 1钛，锆和Ha的1-甲基硼烷苯配合物的合成。TiCl 3（C 5 H 5 BMe），TiCl 2 Cp（C 5 H 5 BMe），ZrCl 2（C 5 H 5 BMe）2和ZrCl 2 Cp *（C 5 H 5 BMe）的结构†

  摘要：

  TiCl 3（C 5 H 5 BMe）（6a），[MCl 3（C 5 H 5 BMe）] x（6b，M = Zr; 6c，M = Hf）和MCl 2（C 5 H 5 BMe） ）2（7b，M = Zr; 7c，M = Hf）由四氯化物MCl 4（M = Ti，Zr，Hf）和Li（C 5 H 5 BMe）（3），2-（Me 3 Si C 5 H 5 BMe（4）或2-（Me 3 Sn）C 5 H 5 BMe（5）的高收率。MCl 2 Cp（C 5 H 5 BMe）（8a，M = Ti; 8b，M = Zr）和MCl 2 Cp *（C 5 H 5 BMe）（9b，M = Zr; 9c，M = Hf）的配合物由相应的环戊二烯基前体MCl 3 Cp（M = Ti，Zr）和MCl 3 Cp *（M = Zr，Hf）相似地制备。氧化还原电势比对应的Cp络合物移动了0.35-0.41 V，以产生更多的阳

  DOI：

  10.1021/om970313b

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.
• Borabenzene Derivatives. 26.¹ Syntheses of 1-Methylboratabenzene Complexes of Titanium, Zirconium, and Hafnium. Structures of TiCl₃(C₅H₅BMe), TiCl₂Cp(C₅H₅BMe), ZrCl₂(C₅H₅BMe)₂, and ZrCl₂Cp*(C₅H₅BMe)
  作者：Gerhard E. Herberich、Ulli Englert、Andreas Schmitz

  DOI：10.1021/om970313b

  日期：1997.8.1

  = Zr, Hf). The redox potentials are shifted by 0.35−0.41 V to more anodic values than those for the corresponding Cp complexes. Molecule 6a shows a piano-stool-type structure, while 7b, 8a, and 9b possess typical bent sandwich structures.

  TiCl 3（C 5 H 5 BMe）（6a），[MCl 3（C 5 H 5 BMe）] x（6b，M = Zr; 6c，M = Hf）和MCl 2（C 5 H 5 BMe） ）2（7b，M = Zr; 7c，M = Hf）由四氯化物MCl 4（M = Ti，Zr，Hf）和Li（C 5 H 5 BMe）（3），2-（Me 3 Si C 5 H 5 BMe（4）或2-（Me 3 Sn）C 5 H 5 BMe（5）的高收率。MCl 2 Cp（C 5 H 5 BMe）（8a，M = Ti; 8b，M = Zr）和MCl 2 Cp *（C 5 H 5 BMe）（9b，M = Zr; 9c，M = Hf）的配合物由相应的环戊二烯基前体MCl 3 Cp（M = Ti，Zr）和MCl 3 Cp *（M = Zr，Hf）相似地制备。氧化还原电势比对应的Cp络合物移动了0.35-0.41 V，以产生更多的阳