lithium [bis(dimethylamino)boryl]cyclopentadienide

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: lithium [bis(dimethylamino)boryl]cyclopentadienide
• 英文别名: lithium (cyclopentadienyl)bis(dimethylamide)borane；Lithium;cyclopenta-2,4-dien-1-ylidene-bis(dimethylamino)boranuide
• 化学式: C₉H₁₆BN₂*Li
• 分子量: 169.991
• InChiKey: WZHXCUPSPRGZFU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.77
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  trichlorotris(tetrahydrofuran)chromium(III) 、 lithium [bis(dimethylamino)boryl]cyclopentadienide 以 四氢呋喃 为溶剂， 反应 12.0h， 以84%的产率得到(η5-cyclopentadienyl)bis(dimethylamide)borane chromium(III) dichloride
  参考文献：
  名称：

  [EN] MONOCYCLOPENTADIENYL COMPLEXES
  [FR] COMPLEXES DU TYPE MONOCYCLOPENTADIENYLE

  摘要：

  单环戊二烯基配合物中，环戊二烯基系统至少带有一个未带电的供体，通过含硼桥键结合，并包含元素周期表第15和/或16族的一个或多个原子，并与选自氧化态为3的钛、钒、铬、钼和钨的金属结合，催化剂系统包括至少一种单环戊二烯基配合物，该催化剂系统用于烯烃的聚合或共聚合，以及在该催化剂系统存在下通过烯烃的聚合或共聚合制备聚烯烃的方法和由此获得的聚合物。

  公开号：

  WO2004018489A1
• 作为产物：
  描述：

  lithium dimethylamide 、 c-C6H9CCB{N(C2H5)2}2 以 四氢呋喃 为溶剂， 以90%的产率得到lithium [bis(dimethylamino)boryl]cyclopentadienide
  参考文献：
  名称：

  Borylcyclopentadienides

  摘要：

  The cyclopentadienylboranes C(5)H(5)BR(2) 1-4 (R = NMe(2), 1/2(OCMe(2))(2), Pr-i, Me) are synthesized from alkali metal cyclopentadienides MCp (M = Li, Na) and BCl(NMe(2))(2), ClB (OCMe(2))(2), BClPr2i, and BBrMe(2), respectively. Compound 1 reacts with lithium dialkylamides (LiNMe(2), LDA, LiTMP) in THF or with elemental sodium to give the salts M[C5H5B(NMe(2))(2)] [M(5) with M = Li, Na]. Compounds 2 and 3 are metalated by LiTMP, and compounds 3 and 4 by cyclopentadienides MCp (M = Li, Na) to give borylcyclopentadienides or boratafulvenes M[C(5)H(5)BR(2)] M(6)-M(8) (R = 1/2(OCMe(2))(2), Pr-i, Me). Estimated (NMR) room temperature equilibrium constants for the systems 1-4/LiCp in THF are 0.5, 4, >300, and >300, respectively; they show that dialkylboryl substituents stabilize cyclopentadienide ions markedly. The triclinic THF solvate Na(THF)(5) (=10) forms an approximately trigonal helix with alternating Na(THF)(+) and anion units, while the tetragonal tetrahydropyran solvate Na(THP)(5) (=11) forms a tetragonal helix. The monoclinic solvate Li(12-crown-4)-(6) (=12) is molecular, and the orthorhombic Na(THP)(2)(8) (=13) displays a chain structure. The B-C1 distances [154.5(2) for 11, 148.8(8) for 12, and 150.8(4) pm for 13], lengthened C1-C2/C1-C5 distances (av) (142.5 for 11, 142.1 for 12, and 143.6 pm for 13), slightly lengthened C3-C4 distances (140.0 for 11, 141.1 for 12, and 143.5 pm for 13), and shortened C2-C3/C4-C5 distances (av) (140.3 for 11, 137.3 for 12, and 137.9 pm for 13) are caused by pi interactions (11 < 12, 13) between the C-5 ring and the boryl function. These interactions are weak in the case of the B(NMe(2))(2) group and quite marked for the B(OCMe(2))(2) and BMe(2) groups.

  DOI：

  10.1021/om950420a