lithium isopropenylcyclopentadienide | 77060-52-7

• 分子结构分类: 有机化合物
• 英文名称: lithium isopropenylcyclopentadienide
• 英文别名: lithium;5-prop-1-en-2-ylcyclopenta-1,3-diene
• CAS: 77060-52-7
• 化学式: C₈H₉*Li
• 分子量: 112.1
• InChiKey: UXUWPLIBTOUGJB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.56
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  lithium isopropenylcyclopentadienide 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 氘代四氢呋喃 、 乙醚 为溶剂， 反应 75.0h， 生成
  参考文献：
  名称：

  有机锂化合物的官能团化学：烯基取代的环戊二烯化锂的光化学[2 + 2]环加成。

  摘要：

  DOI：

  10.1002/anie.200503726
• 作为产物：
  描述：

  (C₅H₄CMe₂CMe₂CN)Li 以 四氢呋喃 、 正戊烷 为溶剂， 反应 0.75h， 生成 lithium isopropenylcyclopentadienide
  参考文献：
  名称：

  螯合环戊二烯基-酮亚胺基配体的第4组金属配合物

  摘要：

  A pendant nitrile group attached to the lithium cyclopentadienide moiety in (C(5)H(4)CM(e)2CMe(2)CN)Li was alkylated using organyl lithium reagents (RLi, R = Ph, t-Bu, Me), giving rise to dianionic cyclopentadienyl-ketimides [C5H(4)CMe(2)CMe(2)C(R)-N]Li-2, which were subsequently utilized as chelating ligands for the synthesis of group 4 bent metallocene or half-sandwich complexes (12 examples of the types [(eta(5)-C5R'5){eta(5)-C5H4CMe2CMe2C(R)-N-eta N}MCl], R' = H or Me, M = Ti, Zr, or Hf, and [{eta(5)-C5H(4)CMe(2)CMe(2)C(R)-N-eta N}TiX2], X = Cl or NMe2, respectively, were prepared and characterized). Consecutive protolysis of the intramolecularly bound ketimide moiety in bent metallocenes afforded pendant imine or cationic iminium moieties, respectively, attached to group 4 organometallic fragments. Selected compounds were used as precatalysts in a preliminary screening for ethylene polymerization activity.

  DOI：

  10.1021/acs.organomet.6b00019

文献信息

• Ring functionalized cyclopentadienyl derivatives of niobium and tantalum: molecular structures of (η5-C5H4−CO2CH3)M(CO)4 where M = Nb and Ta and (η5-C5H4−CO2CH2C6H5)Nb(CO)4
  作者：Thomas E. Bitterwolf、Skip Gallagher、Arnold L. Rheingold、Glenn P.A. Yap

  DOI：10.1016/s0022-328x(97)00225-8

  日期：1997.1

  and tantalum compounds are air-stable as solids but readily undergo oxidation in solution. Compounds were characterized by IR, 1H and 13CNMR spectroscopies, and elemental analyses. Molecular structures of three compounds were determined. (η5-C5H4CO2CH3)Nb(CO)4: monoclinic, P21/c, a = 12.664(6) Å, b = 6.390(3) Å, c, = 15.355(9) Å, β = 97.81(4)°, V = 1231(1) Å3, Z = 4, and R(F) = 3.90%. (η5-C5H4CO2CH3)Ta(CO)4:

  Na = Mb或Ta的Na [M 2（μ-Cl）3（CO）8 ]与NAC 5 H 4 R，其中R = COCH 3，CO 2 CH 3，CO 2 C 2 H 5， COC 6 ħ 5，COCH 2 ç 6 ħ 5，LIC 5 ħ 4 C（CH 3）CH 2，或NAC 9 ħ 7给出了相应的（η 5 -C 5 H ^ 4R）M（CO）4，或（η 5 -C 9 ħ 7）M（CO）4种以良好的收率化合物。NAC 5 ħ 4 COCH 2 C ^ 6 ħ 5，一个新的环戊二烯基合成子，用于制备TLC 5 ħ 4 COCH 2 C ^ 6 ħ 5，和（η 5 -C 5 H ^ 4 COCH 2 C ^ 6 ħ 5）的Mn（CO ）3。后者被充分表征为新配体的模型化合物。铌和钽化合物作为固体具有空气稳定性，但易于在溶液中氧化。通过IR，1 H和13 CNMR光谱以及元素分析对化合物进行表征。确定了三种化合物的分子结构。（η
• Regioselectivity of reactions of vinyl- and isopropenylcyclopentadienide anions with electrophilic agents. Synthesis and crystal structures of complexes [C5H4C(Me)=CH2]ZrCl3 · 2THF and [C5Me4CH=CH2]ZrCl3 · 2THF
  作者：D. P. Krut’ko、M. V. Borzov、O. V. Dolomanov、A. V. Churakov、D. A. Lemenovskii

  DOI：10.1007/s11172-005-0263-y

  日期：2005.2

  Regioselectivity of the reactions of lithium vinyl- and isopropenylcyclopentadienides C5H4C(R)=CH2 -Li+(R = H, Me) and lithium tetramethylvinylcyclopentadienide C5Me4CH=CH2 -Li+ with various electrophilic agents (Me3SiCl, Me3SnCl, Et2PCl, 2-chloro-1, 3-dioxaphospholane, and MeI) was studied. Two new monocyclopentadienyl zirconium complexes, [C5H4C(Me) = CH2]ZrCl3 · 2THF and [C5Me4CH=CH2]ZrCl3 · 2THF, were synthesized. Their crystal structures were established by X-ray diffraction. The results of quantum chemical calculations for the C5H4C(R) = CH2 - (R = H, Me) and C5Me4CH=CH2 - anions by the DFT method (RMPW1PW91) with the 6-311+G(d, p) split valence basis set are in good agreement with experimental data on the regioselectivity of their reactions with electrophilic agents.

  研究了乙烯基和异丙烯基环戊二烯锂 C5H4C(R)=CH2-Li+（R = H，Me）和四甲基乙烯基环戊二烯锂 C5Me4CH= -Li+ 与各种亲电剂（Me3SiCl、Me3SnCl、Et2PCl、2-氯-1，3-二氧磷杂环戊烷和 MeI）反应的区域选择性。合成了两种新的单环戊二烯锆配合物，即 [C5H4C(Me) = ]ZrCl3 - 2THF 和 [C5Me4CH= ]ZrCl3 - 2THF。通过 X 射线衍射确定了它们的晶体结构。采用 6-311+G(d, p) 分裂价基集的 DFT 方法 (RMPW1PW91) 对 C5H4C(R) = - (R = H, Me) 和 C5Me4CH= - 阴离子进行量子化学计算的结果与它们与亲电剂反应的区域选择性实验数据十分吻合。
• Synthesis and reactivity of metal-containing monomers. Part 59. Preparation and polymerization transformations of vinyl and isopropenyl derivatives of hafnocene dichloride
  作者：D. P. Krut’ko、M. V. Borzov、D. A. Lemenovskii、G. I. Dzhardimalieva、A. D. Pomogailo

  DOI：10.1007/s11172-005-0244-1

  日期：2005.1

  hafnium(IV), [C5H4(CR=CH2)]2HfCl2[R = H (5), CH3 (6)], were prepared and characterized. The organometallic monomers obtained were shown to undergo radical or anionic homopolymerization. Copolymerization of these metallocenes with styrene was performed. The potential applications of the metal polymers in question were considered.

  制备并表征了铪 (IV)、[C5H4(CR=CH2)]2HfCl2[R=H(5)、CH3(6)] 的新型乙烯基和异丙烯基取代环戊二烯基配合物。获得的有机金属单体显示出经历自由基或阴离子均聚。进行这些茂金属与苯乙烯的共聚。考虑了所讨论的金属聚合物的潜在应用。
• A new, general route to .eta.5-vinylcyclopentadienyl organometallic monomers
  作者：David W. Macomber、William P. Hart、Marvin D. Rausch、Ralph D. Priester、Charles U. Pittman

  DOI：10.1021/ja00367a055

  日期：1982.2
• Reactions of [(diphenylphosphino)methyl]lithium with dimethylfulvene
  作者：N. E. Schore、B. E. LaBelle

  DOI：10.1021/jo00324a019

  日期：1981.5