[1,3-C3H6(NSiMe3)2]2Zr | 172609-45-9

• 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: [1,3-C3H6(NSiMe3)2]2Zr
• 英文别名: [CH2(CH2NSiMe3)2]2Zr；Zr(Me3SiN(CH2)3NSiMe3)2；trimethylsilyl(3-trimethylsilylazanidylpropyl)azanide;zirconium(4+)
• CAS: 172609-45-9
• 化学式: C₁₈H₄₈N₄Si₄Zr
• 分子量: 524.172
• InChiKey: PYTKQGUKNPYSBW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.16
• 重原子数：
  27.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.96
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  1,3-bis<(trimethylsilyl)amino>propane 、 氯化锆(IV) 在 BuLi 作用下， 以 正己烷 、 甲苯 为溶剂， 以88%的产率得到[1,3-C3H6(NSiMe3)2]2Zr
  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

• Zirconium(IV) Complexes Having a Rigid 1,8-Naphthalene Diamide versus a Flexible 1,3-Propylene Diamide for Olefin Polymerization
  作者：Choong Hoon Lee、Young-Hye La、Joon Won Park

  DOI：10.1021/om990360z

  日期：2000.2.1

  Structure and chemical properties of zirconium(IV) complexes containing a rigid naphthalene diamide ligand ([1,8-C10H6(NSiMe3)2]2-) or flexible propylene diamide ligands ([1,3-C3H6(NR)2]2-, R = SiMe3, Si(i-Pr)3) are described. The reaction of 1,8-C10H6(NHSiMe3)2 with Zr(NMe2)4 in refluxing toluene yields [1,8-C10H6(NSiMe3)2]Zr(NMe2)2 (1), and the product 1 is converted to [1,8-C10H6(NSiMe3)2]ZrCl2

  锆的结构和化学特性（IV）含有刚性萘二酰胺配位体（[1,8-C复合物10 ħ 6（NSiMe 3）2 ] 2 - ）或柔性的丙烯二酰胺配位体（[1,3-C 3 H ^ 6（NR）2 ] 2 -，R =森达3，硅（我-Pr）3）进行说明。1,8-C 10 H 6（NHSiMe 3）2与Zr（NMe 2）4在回流的甲苯中反应生成[1,8-C 10 H6（NSiMe 3）2 ] Zr（NMe 2）2（1），并且产物1通过适当的分离产率被转化为[1,8-C 10 H 6（NSiMe 3）2 ] ZrCl 2（2）。用过量的ClSiMe 3处理。X射线晶体学分析确定2形成通过固态的两个氯化物桥缔合的二聚体，并具有高度褶皱的六元环，且N-Zr-N咬合角较小（91.05°）。1,3-C 3 H 6（NHR）2的反应（R ＝ SiMe 3，Si（i- Pr）3）和Zr（NMe 2）4也提供[1，3-C 3
• Synthesis and molecular structures of zirconium complexes that contain bidentate amido ligands
  作者：Matthew D. Lococo、Han Lee、Richard F. Jordan

  DOI：10.1016/j.molstruc.2008.11.026

  日期：2009.2

  Abstract Zirconium complexes that contain bidentate amido ligands, Zr2EtN(CH2)3NEt}4 (1), Zr2PhN(CH2)2NPh}4 (2), ZrMe3SiN(CH2)3NSiMe3}2 (3) and Zrtrans-N,N′-diphenyl-1,2-diaminocyclohexane}Cl2(THF)2 (4), have been prepared by the reaction of lithium diamido reagents with ZrCl4, and characterized by single crystal X-ray diffraction. The molecular structures of complexes 1–4 are discussed.

  摘要 含有双齿酰胺基配体 Zr2EtN(CH2)3NEt}4 (1)、Zr2PhN( )2NPh}4 (2)、ZrMe3SiN( )3NSiMe3}2 (3) 和 Zr反式-N,N'-二苯基-1,2-二氨基环己烷}Cl2(THF)2 (4)，由二氨基锂试剂与ZrCl4反应制备，并通过单晶X射线衍射表征。讨论了配合物 1-4 的分子结构。
• Chelate-Controlled Synthesis of <i>rac-</i> and <i>meso-</i>Me₂Si(3-^tBu-C₅H₃)₂ZrCl₂
  作者：Matthew D. LoCoco、Richard F. Jordan

  DOI：10.1021/om034184c

  日期：2003.12.1

  The reaction of the chelated bis-amide complex ZrPhN(CH2)(3)NPh}Cl-2(THF)(2) (2) with Li-2[Me2Si(3-Bu-t-C5H3)(2)] yields meso-Me2Si(3-Bu-t-C5H3)(2)ZrPhN(CH2)(3)NPh} (meso-3) in > 98% yield. In contrast, the reaction of ZrMe3SiN(CH2)(3)NSiMe3}Cl-2(THF)(2) (4) or the related mono-THF adduct ZrMe3SiN(CH2)(3)NSiMe3}Cl-2(THF) (5) with Li-2[Me2Si(3-Bu-t-C5H3)(2)] yields rac-Me2Si(3-Bu-t-C5H3)(2)ZrMe3SiN(CH2)(3)NSiMe3} (rac-6) in quantitative NMR yield and 89% isolated yield. X-ray crystallographic analyses show that the ZrRN(CH2)(3)NR} chelate ring in rac-6 has a pronounced twist conformation, while that in meso-3 has a flatter, envelope conformation. It is proposed that the conformations of the ZrRN(CH2)(3)NR} chelate rings in the stereodetermining transition states for addition of the second Cp- ring in these reactions are similar to those in the metallocene products and control the diastereoselectivity. meso-3 and rac-6 are converted to meso-Me2Si(3-Bu-t-C5H3)(2)ZrCl2 (meso-1) and rac-1, respectively, by reaction with HCl in Et2O.