Zr(Me3SiN(CH2)3NSiMe3)Cl2(THF)2 | 172609-47-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: Zr(Me3SiN(CH2)3NSiMe3)Cl2(THF)2
• 英文别名: Dichlorozirconium(2+);oxolane;trimethylsilyl(3-trimethylsilylazanidylpropyl)azanide
• CAS: 172609-47-1
• 化学式: C₁₇H₄₀Cl₂N₂O₂Si₂Zr
• 分子量: 522.818
• InChiKey: CZZXQUWZRAFGIH-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.76
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  K{Ru(η5-C5H5)(CO)2} 、 Zr(Me3SiN(CH2)3NSiMe3)Cl2(THF)2 以 四氢呋喃 为溶剂， 以73%的产率得到
  参考文献：
  名称：

  Gade, Lutz H., Inorganic Chemistry, 1999, vol. 38, # 23, p. 5295 - 5307

  摘要：

  DOI：
• 作为产物：
  描述：

  [1,3-C3H6(NSiMe3)2]2Zr 以 四氢呋喃 、 甲苯 为溶剂， 生成 Zr(Me3SiN(CH2)3NSiMe3)Cl2(THF)2
  参考文献：
  名称：

  在新的含无支撑Zr-M键的Zr-M杂双金属化合物中使用锆半三明治复合物作为构建基（M = Fe，Ru，Co）

  摘要：

  A new class of Zr-M heterobimetallic complexes (M = Fe, Ru, Co) containing the {CH2(CH(2)NSiMe(3))(2)(Cp)Zr} fragment as a building block has been synthesized by salt metathesis of CH2(CH(2)NSiMe(3))(2)(Cp)ZrCl (5) with K[CpM'(CO)(2)] (M' = Fe, Ru) and Na[Co(CO)(3)(PR(3))] (R = Ph, Tol). The zirconium half-sandwich complex 5 was obtained in four reaction steps from ZrCl4 via the spirocyclic complex [CH2(CH(2)NSiMe(3))(2)]Zr-2 (1), the (diamido)dichlorozirconium complex CH2(CH(2)NSiMe(3))(2)ZrCl2 (2), and its soluble THF-adduct CH2(CH(2)NSiMe(3))(2)ZrCl2(THF)(2) (3). The latter was converted to 5 in good yield by reaction with LiCp. The Zr-Fe heterodinuclear complex CH2(CH(2)NSiMe(3))(2)(Cp)Zr-Fe(CO)(2)Cp (6) has been characterized by X-ray crystal structure analysis which has established the presence of an unsupported Zr-Fe bond. The nu(CO) infrared bands of the CpM'(CO)(2) moieties in the Zr-M' complexes (M' = Fe, Ru) indicate a significant ionic contribution to the Zr-M' bonding.

  DOI：

  10.1021/om00011a060

文献信息

• Control of <i>ansa</i>-Zirconocene Stereochemistry by Reversible Exchange of Cyclopentadienyl and Chloride Ligands
  作者：Richard M. Buck、Nawaporn Vinayavekhin、Richard F. Jordan

  DOI：10.1021/ja0681523

  日期：2007.3.1

  to pure rac. The isomerization requires Cp−enantioface exchange and is catalyzed by chloride ion, which reversibly displaces Cp- from Me2Si(3-R-C5H3)2ZrMe3SiN(CH2)3NSiMe3}. Kinetic analyses for selected complexes showed first-order dependence of the isomerization rate on both metallocene and chloride concentrations. Reversible Cp-/Cl- exchange is also facile for ansa-bis-Cp}ZrCl2 and nonbridged Cp2ZrCl2

  Li2[Me2Si(3-R-C5H3)2]盐与ZrMe3SiN(CH2)3NSiMe3}Cl2(THF)2在THF中反应定量得到外消旋Me2Si(3-R-C5H3)2ZrMe3SiN(CH2)具有 100% 立体选择性的 3NSiMe3} 锆茂。核磁共振监测研究表明，这些反应最初形成外消旋/内消旋混合物，经过异构化成为纯外消旋。异构化需要 Cp-enantioface 交换，并由氯离子催化，从 Me2Si(3-R-C5H3)2ZrMe3SiN(CH2)3NSiMe3} 可逆地置换 Cp-。所选配合物的动力学分析显示异构化速率对茂金属和氯化物浓度的一级依赖性。可逆 Cp-/Cl- 交换对于 ansa-bis-Cp}ZrCl2 和非桥连 Cp2ZrCl2 复合物也很容易。
• Syntheses of rac/meso-{PhP(3-t-Bu-C5H3)2}-Zr{RN(CH2)3NR}, structural analyses of rac-{PhP(3-t-Bu-C5H3)2}Zr{RN(CH2)3NR} (where R is SiMe3 or Ph), and meso to rac isomerization
  作者：Jonathan C. Axtell、Susan D. Thai、Laurel A. Morton、William S. Kassel、William G. Dougherty、Deanna L. Zubris

  DOI：10.1016/j.jorganchem.2008.09.018

  日期：2008.12

  ZrRN(CH2)3NR}Cl2(THF)2 (where R = SiMe3 or Ph, respectively) using ethereal solvent. These isomeric pairs were characterized by 1H, 13C1H}, and 31P1H} NMR spectroscopy; rac-3 and rac-4 were also examined via single crystal X-ray crystallography. The structures of rac-3 and rac-4 are notable in the tendency of the cyclopentadienyl rings towards η3 coordination. While isolated samples of rac-3/meso-3 and rac-4/meso-4

  的合成外消旋/内消旋- PHP（3-吨-Bu-C 5 H ^ 3）2 } Zr的我3的SiN（CH 2）3 NSiMe 3 }（外消旋-3 /内消旋-3）和外消旋/内消旋- PhP（3- t -Bu-C 5 H 3）2 } Zr PhN（CH 2）3 NPh}（rac -4 / meso -4）通过K 2 [PhP（3- t -Bu- C 5 H 3）2 ]·1.3 THF（2）和Zr RN（CH 2）3 NR} Cl 2（THF）2（其中R = SiMe 3或Ph分别），使用醚溶剂。这些同分异构对通过1 H，13 C 1 H}和31 P 1 H} NMR光谱进行表征。还通过单晶X射线晶体学检查了rac -3和rac -4。的结构外消旋-3和外消旋-4是在环戊二烯基环的朝向η的倾向显着3协调。分离的rac -3 / meso -3和rac -4 / meso -4样品在四氢呋喃-d
• A Chelate-Amidozirconium Fragment as Building Block for Unsupported Trinuclear ZrM2 Heterobimetallic Complexes(M= Fe, Ru, Co)
  作者：Stefan Friedrich、Lutz H. Gade、Ian J. Scowen、Mary McPartlin

  DOI：10.1002/anie.199613381

  日期：1996.7.9
• Gade, Lutz H., Inorganic Chemistry, 1999, vol. 38, # 23, p. 5295 - 5307
  作者：Gade, Lutz H.

  DOI：——

  日期：——
• Using Zirconium Half-Sandwich Complexes as Building Blocks in a New Class of Zr-M Heterobimetallics Containing Unsupported Zr-M Bonds (M = Fe, Ru, Co)
  作者：Stefan Friedrich、Lutz H. Gade、Ian J. Scowen、Mary McPartlin

  DOI：10.1021/om00011a060

  日期：1995.11

  A new class of Zr-M heterobimetallic complexes (M = Fe, Ru, Co) containing the CH2(CH(2)NSiMe(3))(2)(Cp)Zr} fragment as a building block has been synthesized by salt metathesis of CH2(CH(2)NSiMe(3))(2)(Cp)ZrCl (5) with K[CpM'(CO)(2)] (M' = Fe, Ru) and Na[Co(CO)(3)(PR(3))] (R = Ph, Tol). The zirconium half-sandwich complex 5 was obtained in four reaction steps from ZrCl4 via the spirocyclic complex [CH2(CH(2)NSiMe(3))(2)]Zr-2 (1), the (diamido)dichlorozirconium complex CH2(CH(2)NSiMe(3))(2)ZrCl2 (2), and its soluble THF-adduct CH2(CH(2)NSiMe(3))(2)ZrCl2(THF)(2) (3). The latter was converted to 5 in good yield by reaction with LiCp. The Zr-Fe heterodinuclear complex CH2(CH(2)NSiMe(3))(2)(Cp)Zr-Fe(CO)(2)Cp (6) has been characterized by X-ray crystal structure analysis which has established the presence of an unsupported Zr-Fe bond. The nu(CO) infrared bands of the CpM'(CO)(2) moieties in the Zr-M' complexes (M' = Fe, Ru) indicate a significant ionic contribution to the Zr-M' bonding.