dimethylazanide;3-[2-(3H-inden-3-id-1-yl)ethyl]-1H-inden-1-ide;zirconium(4+) | 174175-83-8

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: dimethylazanide;3-[2-(3H-inden-3-id-1-yl)ethyl]-1H-inden-1-ide;zirconium(4+)
• CAS: 174175-83-8；181228-37-5
• 化学式: C₂₄H₂₈N₂Zr
• 分子量: 435.724
• InChiKey: WNHWZSFETJYUSP-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：
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• 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：

  dimethylazanide;3-[2-(3H-inden-3-id-1-yl)ethyl]-1H-inden-1-ide;zirconium(4+) 、 三氟甲磺酸 以 甲苯 为溶剂， 生成 rac-[(C2H4(C9H6)2)2Zr(OTf)2]
  参考文献：
  名称：

  ansa-Zirconocene Ester Enolates：合成、结构、与有机路易斯酸的反应以及在甲基丙烯酸酯聚合中的应用

  摘要：

  报告了与甲基丙烯酸酯的同种特异性聚合相关的 ansa-zirconocene 酯烯醇化物配合物的合成、结构表征和抽象化学。外消旋-(EBI)ZrMe(OTf) 和外消旋-(EBI)Zr(OTf)(2) [EBI = C(2)H(4)(Ind)(2)] 与 1 和 2 当量的异丙基异丁酸锂的反应在甲苯中产生 ansa-锆茂单和二酯烯醇化物复合物的第一个例子：rac-(EBI)ZrMe[OC(O(i)Pr)=CMe(2)] (1) 和 rac-(EBI)Zr[OC (O(i)Pr)=CMe(2)](2) (2) 的分离产率分别为 89% 和 50%。在六种不同的有机溶剂中研究了 1 与 B(C(6)F(5))(3) 的反应；在环境温度下的 THF 中，该反应干净地产生了可分离的阳离子型正二茂锆酯烯醇化物络合物 rac-(EBI)Zr(+)(THF)[OC(O(i)Pr)=CMe(2)][MeB(C)

  DOI：

  10.1021/ja031558k
• 作为产物：
  描述：

  ZrCl2(NMe2)2(1,2-dimethoxyethane) 、 Li2[1,2-ethylene-bis(indenyl)](Et2O) 以 甲苯 为溶剂， 以50%的产率得到dimethylazanide;3-[2-(3H-inden-3-id-1-yl)ethyl]-1H-inden-1-ide;zirconium(4+)
  参考文献：
  名称：

  1,3-双桥联的第4族茂金属通过侧链烯烃的分子内还原偶联

  摘要：

  新的前体M（NMe 2）2 Cl 2（dme）（M = Zr（3），Hf（4））与带有4-戊烯基侧基的甲硅烷基桥接双（1-茚基）配体的二锂衍生物反应在-35°C下于甲苯中的Li 2 [ 3,3'- 5 R 2 -SBI]（2）提供相应的rac /内消旋比为6-7：1的双（二甲基氨基）金属茂。在催化量的无水HCl存在下，在二氯甲烷中用过量的TMS-Cl处理基本上富含rac的锆茂混合物，得到rac- [3,3'- 5R 2 -SBI] ZrCl 2（7）的分离产率为40％，不含内消旋异构体。Li 2 [SBI]·OEt 2和Li 2 [EBI]·OEt 2与3和4的相似反应也导致选择性形成rac /介孔比为[SBI]高达20：1的rac-茂金属Zr（NMe 2）2（10）。rac- [3,3'- 5 R 2 -SBI] ZrCl 2（7的钠汞齐还原）在THF中导致悬垂烯烃的分子内尾-尾偶联，以

  DOI：

  10.1021/om9905411

文献信息

• Aluminum <i>ansa</i>-Indenyl Compounds. Synthesis, Structures, Dynamic Properties, and Application in the Synthesis of Group 4 <i>ansa</i>-Metallocenes
  作者：B. Thiyagarajan、Richard F. Jordan、Victor G. Young

  DOI：10.1021/om990381t

  日期：1999.12.1

  (4b), or 1,2-3-AlMe2(THF)-1-indenyl}2-C2H4 (5), respectively, as colorless to pale yellow solids in 41−70% isolated yields. Compounds 2a and 4b are isolated as the rac isomers, whereas 1 and 3 are isolated as rac/meso mixtures from which the rac isomer can be separated by recrystallization. Compound 5 was isolated as a single diastereomer of 1,2-3-AlMe2(THF)-1-indenyl}2-C2H4. The molecular structures

  描述了铝ansa-双（茚基）化合物的合成，结构，动力学性质和茚基转移反应。2当量的AlMe 2 Cl与1当量的Li 2 [（1-茚基）2 SiMe 2 ]，Li 2 [（2-Me-​​1-茚基）2 SiMe 2 ]，Li 2 [（2-Me -4,5-苯并-1-茚基）2 SiMe 2 ]·Et 2 O，Li 2 [（2-Me-​​4-Ph-1-茚基）2 SiMe 2 ]·Et 2 O或Li 2 [1 ，2-（3-茚基）2 -C 2 H4 ]在Et 2 ö随后通过与合适的路易斯碱（L）处理，得到阿尔梅2（THF）（茚基）} 2森达2（1），[1-阿尔梅2（1,4-二恶烷）0.5 - 2-Me-​​1-茚基} 2 SiMe 2 ] n（2a），1-AlMe 2（Et 2 O）-2-Me-​​4,5-benz-1-indenyl} 2 SiMe 2（3）， 1-AlMe 2（Et 2 O）-2-Me-​​4-Ph-1-茚基}
• Efficient Synthesis of rac-(Ethylenebis(indenyl))ZrX2 Complexes via Amine Elimination
  作者：Gary M. Diamond、Stephan Rodewald、Richard F. Jordan

  DOI：10.1021/om00001a003

  日期：1995.1

  The amine elimination reaction of 1,2-bis(3-indenyl)ethane (3) and Zr(NMe(2))(4) (2) affords pure rac-(EBI)Zr(NMe(2))(2) (4; EBI = 1,2-ethylenebis(1-indenyl)) in. 68% isolated yield. Treatment of 4 with 2 equiv of Me(2)-NH.HCl affords rac-(EBI)ZrCl2 (1) in 92% isolated yield. Compound 1 can, also be prepared directly from 2 and 3 in a ''one-pot'' synthesis in 69% isolated yield.
• Efficient Synthesis of Chiral <i>ansa</i>-Metallocenes by Amine Elimination. Synthesis, Structure, and Reactivity of <i>rac</i>-(EBI)Zr(NMe₂)₂
  作者：Gary M. Diamond、Richard F. Jordan、Jeffrey L. Petersen

  DOI：10.1021/ja9604830

  日期：1996.1.1

  The amine elimination reaction of Zr(NMe(2))(4) (2) and (EBI)H-2 (1,2-bis(3-indenyl)ethane, 3) in toluene at 100 degrees C affords pure rac-(EBI)Zr(NMe(2))(2) (rac-4, EBI=ethylene-1,2-bis(1-indenyl)) in 68% isolated yield. This reaction proceeds via the rapidly formed mono-indenyl intermediate (eta(5)-C9H6CH2CH2C9H7)Zr(NMe(2))(3) (6) which undergoes reversible intermolecular amine elimination with a second equivalent of 2 to give the binuclear species (mu-eta(5),eta(5)-EBI)Zr(NMe(2))(3)}(2) (5, rac and meso isomers) or reversible intramolecular amine elimination to give either rac-4 or meso-4. The kinetic metallocene product is a 1/1 mixture of rac-4 and meso-4, the thermodynamic product is rac-4, and the meso-4 to rac-4 isomerization is catalyzed by the NMe(2)H co-product. The rac-4/meso-4 product ratio can be controlled by adjusting the rate of NMe(2)H removal from the reaction vessel and the steady state concentration of amine in the reaction mixture. The molecular structure of me-4 has been determined by X-ray crystallography. rac-4 is converted to rac-(EBI)ZrCl2 (rac-1) in high yield by reaction with NMe(2)H . HCl (92% isolated) or Me(3)SiCl (quantitative). The syntheses of 2, rac-4, and rac-1 can be combined in a ''one pot'' synthesis of rac-1 from ZrCl4 in 68% overall yield. Alkylation of rac-4 with AlMe(3) affords rac-(EBI)ZrMe(2) (rac-7) in 90%, isolated yield. rac-4 can be used directly as a catalyst precursor for the isospecific polymerization of propylene.