di(inden-1-id-1-yl)-dimethylsilane;dimethylazanide;zirconium(4+) | 174081-14-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: di(inden-1-id-1-yl)-dimethylsilane;dimethylazanide;zirconium(4+)
• CAS: 174081-14-2；181492-71-7
• 化学式: C₂₄H₃₀N₂SiZr
• 分子量: 465.825
• InChiKey: HRPONHATEAIZEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• 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

• 作为产物：
  描述：

  ZrCl2(NMe2)2(1,2-dimethoxyethane) 、 Li2[Me2Si(indenyl)2](Et2O) 以 甲苯 为溶剂， 以66%的产率得到di(inden-1-id-1-yl)-dimethylsilane;dimethylazanide;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}
• Synthesis, Structure, and Reactivity of <i>rac</i>-Me₂Si(indenyl)₂Zr(NMe₂)₂
  作者：Joseph N. Christopher、Gary M. Diamond、Richard F. Jordan、Jeffrey L. Petersen

  DOI：10.1021/om960104b

  日期：1996.9.17

  Me2Si(1-indenyl)2) and Zr(NMe2)4 (2) affords rac-(SBI)Zr(NMe2)2 (4) in 65% isolated yield. This reaction proceeds via initial formation of a mono(indenyl) intermediate, (η5-C9H6SiMe2C9H7)Zr(NMe2)3 (6). Intermediate 6 reacts reversibly with a second equivalent of 2 to form a binuclear complex, μ-η5:η5-Me2Si(1-indenyl)2}Zr(NMe2)3}2 (5), which was prepared independently by the reaction of 3 and 2 equiv of 2. Complex

  （SBI）H 2（3，Me 2 Si（1-茚基）2）和Zr（NMe 2）4（2）的胺消除反应在65中产生rac-（SBI）Zr（NMe 2）2（4）分离产率％。该反应通过最初形成的单（茚基）中间体，（η前进5 -C 9 ħ 6森达2 Ç 9 ħ 7）的Zr（NME 2）3（6）。中级6与第二当量的起反应可逆地2，以形成双核配合物，μ-η 5：η 5 -Me 2的Si（1 -茚基）2 } 锆（NME 2）3 } 2（5独立地制备），通过3和2当量的2的反应。配合物6也经历了可逆的分子内胺消除形成rac - 4和meso - 4。6和4 + NMe 2 H之间的平衡非常有利6。rac - 4是分子内胺消除6的动力学产物，热力学rac - 4 / meso - 4的比率为4/1，而rac - 4 / meso - 4的异构化是由NMe 2 H催化的。从反应混合物中除去NMe 2 H是控制4的收率和rac
• Ansa-bis(indenyl) dimethylamido zirconocenes
  作者：Alexander Vogel、Thomas Priermeier、Wolfgang A. Herrmann

  DOI：10.1016/s0022-328x(96)06683-1

  日期：1997.1

  Tetrakis(dimethylamido)zirconium (3) reacts with dimethylsilylene and isopropylene-bridged bis(indenyl) ligands 4 and 5 to yield the corresponding ansa-bis(dimethylamido)zirconocenes rac-1 and rac-2 containing η5-coordinated π-aromatic ligand systems.

  四（二甲基酰氨基）锆（3）反应以二甲基亚甲硅烷和异丙基-桥连的双（茚基）配体4和5，得到相应的柄型-双（二甲氨基）二茂锆外消旋- 1和外消旋- 2含有η 5配位的π芳族配体系统。
• Synthesis, Structure, Dynamic Properties, and Indenyl Transfer Reactions of {AlMe₂(THF)(indenyl)}₂SiMe₂
  作者：B. Thiyagarajan、Richard F. Jordan、Victor G. Young

  DOI：10.1021/om971072a

  日期：1998.2.1

  The reaction of Li2SBI (SBI = Me2Si(1-indenyl)(2)) with 2 equiv of AlMe2Cl in Et2O, followed by treatment with THF, affords AlMe2(THF)(indenyl)}(2)-SiMe2 (1), which is isolated as a ca. 1/1 mixture of rac and meso isomers, from which rac-1 is obtained by crystallization from toluene. An. X-ray crystallographic analysis establishes that rac-1 exists as the 1,3 isomer, i.e., (1-AlMe2(THF)-1-indenyl)}(3-AlMe2(THF)}-1-indenyl)SiMe2 in the solid state. NMR studies establish that in toluene-d(8), rac-1 exists as a 2/1 mixture of 1,3 and 1,1 Al-indenyl isomers which interconvert rapidly on the NMR time scale at room temperature. Rac-1 undergoes slow isomerization to a 1/1 rac/meso mixture (3 days, 23 degrees C, benzene) and also undergoes slow partial disproportionation by ligand redistribution (28% conversion, 2 days, 23 degrees C, benzene). Compound 1 (1/1 to 1.4/1 rac/meso mixture) reacts with Zr(NMe2)(4) and Hf(NMe2)(4) under mild conditions to yield (SBI)Zr(NMe2)(2) in >90% NMR yield (rac/meso = 4.5/1) and rac-(SBI)Hf(NMe2)(2) in 61% isolated yield, respectively.