(C5H4CMe2CH2CN)Li | 1309569-80-9

• 英文名称: (C5H4CMe2CH2CN)Li
• CAS: 1309569-80-9
• 化学式: C₁₀H₁₂LiN
• 分子量: 153.153
• InChiKey: GBLNYBACJYXWDH-UHFFFAOYSA-N

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：

  三甲基氯硅烷 、 (C5H4CMe2CH2CN)Li 生成
  参考文献：
  名称：

  具有腈侧基的第4组茂金属配合物

  摘要：

  一个新的官能化的环戊二烯基的配体的制备带有腈侧取代基，（C 5 H ^ 4 CME 2 CH 2 CN）-报道。通过原位锂化乙腈与6,6-二甲基富勒烯的反应制备该配体（1）的相应锂盐。所述配体随后被用于第4族金属配合物的合成[（η 5 -C 5 H ^ 4 CME 2 CH 2 CN）2的MC1 2 ]（M =的Ti，2 ; M =锆，3 ; M = HF，  4），[（η 5 -C 5 H ^ 5）（η 5 -C 5 H ^ 4 CME 2 CH 2 CN）的MC1 2 ]（M =的Ti，7 ; M =锆，8），和[（η 5 -C 5我5）（η 5  ç 5 ħ 4 CME 2 CH 2 CN）2的ZrCl 2 ]（9）。到替代路线2包括半夹心络合物的制备[（η 5 -C 5 H ^4 CMe 2 CH 2 CN）TiCl 3 ]（6）。通过共同的光谱方法和复合物的固态结构制备的化合物进

  DOI：

  10.1016/j.jorganchem.2011.02.032
• 作为产物：
  描述：

  6,6-二甲基-5-亚甲基-1,3-环戊二烯 、 乙腈 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以98%的产率得到(C5H4CMe2CH2CN)Li
  参考文献：
  名称：

  具有腈侧基的第4组茂金属配合物

  摘要：

  一个新的官能化的环戊二烯基的配体的制备带有腈侧取代基，（C 5 H ^ 4 CME 2 CH 2 CN）-报道。通过原位锂化乙腈与6,6-二甲基富勒烯的反应制备该配体（1）的相应锂盐。所述配体随后被用于第4族金属配合物的合成[（η 5 -C 5 H ^ 4 CME 2 CH 2 CN）2的MC1 2 ]（M =的Ti，2 ; M =锆，3 ; M = HF，  4），[（η 5 -C 5 H ^ 5）（η 5 -C 5 H ^ 4 CME 2 CH 2 CN）的MC1 2 ]（M =的Ti，7 ; M =锆，8），和[（η 5 -C 5我5）（η 5  ç 5 ħ 4 CME 2 CH 2 CN）2的ZrCl 2 ]（9）。到替代路线2包括半夹心络合物的制备[（η 5 -C 5 H ^4 CMe 2 CH 2 CN）TiCl 3 ]（6）。通过共同的光谱方法和复合物的固态结构制备的化合物进

  DOI：

  10.1016/j.jorganchem.2011.02.032

文献信息

• Synthetic transformations of a pendant nitrile moiety in group 4 metallocene complexes
  作者：Jiří Pinkas、Ivana Císařová、Jiří Kubišta、Michal Horáček、Martin Lamač

  DOI：10.1039/c3dt50209k

  日期：——

  Functional group transformations at the group 4 metallocene framework have been demonstrated, which have provided relatively straightforward access to otherwise synthetically challenging derivatives. The pendant nitrile group in Ti and Zr metallocene complexes of the type [(η5-C5Me5)(η5-C5H4CMe2CH2CN)MCl2] was converted into an intramolecularly bound ketimido moiety by alkylation, which took place not only at the nitrile, but also at the metal centre. The choice of an alkylating reagent (alkyl/aryl lithium, Grignard reagent) was crucial: e.g., 2 equiv. of MeMgBr effected the alkylation only at the metal, yielding selectively complexes [(η5-C5Me5)(η5-C5H4CMe2CH2CN)MMe2], while the use of PhMgBr, PhLi, or MeLi instead gave selectively the ketimido complexes. Organyl lithium reagents were, however, not compatible with the titanocene derivatives. The metal-bound ketimides were subsequently cleaved off by the reaction with HCl, which afforded metallocene dichlorides with a pendant imino group. These compounds were easily protonated again at the nitrogen atom to produce a cationic iminium moiety. Aqueous hydrolysis of the imine or its respective hydrochloride proved to be viable in the case of Zr and it finally afforded a pendant ketone group attached to the zirconocene framework.

  在4族金属烯框架上，功能团转化的示范已经提供了相对简单的途径来获取在合成上具有挑战性的衍生物。类型为[(η5-C5Me5)(η5-C5H4CMe2CH2CN)MCl2]的钛和锆金属烯复合物中的悬挂腈基通过烷基化转化为分子内结合的酮亚胺基团，这一过程不仅发生在腈基上，还发生在金属中心上。烷基化试剂（烷基/芳基锂、格里格纳试剂）的选择至关重要：例如，2当量的MeMgBr仅在金属上进行烷基化，选择性地生成复合物[(η5-C5Me5)(η5-C5H4CMe2CH2CN)MMe2]，而使用PhMgBr、PhLi或MeLi则选择性地产生酮亚胺复合物。然而，芳基锂试剂与钛烯衍生物相容性差。金属结合的酮亚胺随后通过与HCl反应被裂解，生成具有悬挂亚氨基的金属烯二氯化物。这些化合物可以在氮原子上轻易地被质子化，生成阳离子亚氨基团。在锆的情况下，对亚胺或其相应氯化氢的水解被证明是可行的，最终产生一个附着在锆烯框架上的悬挂酮基。
• Group 4 Metal Complexes of Chelating Cyclopentadienyl-ketimide Ligands
  作者：Miloš Večeřa、Vojtech Varga、Ivana Císařová、Jiří Pinkas、Pavel Kucharczyk、Vladimír Sedlařík、Martin Lamač

  DOI：10.1021/acs.organomet.6b00019

  日期：2016.3.14

  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.
• Synthesis and Catalytic Activity of [Cp′Co(COD)] Complexes Bearing Pendant N-Containing Groups
  作者：Indre Thiel、Martin Lamač、Haijun Jiao、Anke Spannenberg、Marko Hapke

  DOI：10.1021/om400330x

  日期：2013.6.10

  The novel Co(I)-complex [(CpCo)-Co-CN(COD)] (Cp-CN = eta(5)-(C5H4CMe2CH2CN), COD = 1,5-cyclooctadiene; 3) with a substituted cyclopentadienyl ligand containing a pendant nitrile moiety has been synthesized and characterized by X-ray diffraction. The reactivity of the nitrile group in 3 has been investigated regarding its behavior in cyclization reactions with alkynes, leading to three new complexes containing pendant 2-pyridyl groups. All synthesized complexes have been evaluated as catalysts in the [2 + 2 + 2] cycloaddition reaction of 1,6-heptadiyne and benzonitrile.