monochlorotris[bis(trimethylsilyl)amido] zirconium | 69897-59-2

• 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: monochlorotris[bis(trimethylsilyl)amido] zirconium
• 英文别名: Bis(trimethylsilyl)azanide;zirconium(4+);chloride；bis(trimethylsilyl)azanide;zirconium(4+);chloride
• CAS: 69897-59-2
• 化学式: C₁₈H₅₄ClN₃Si₆Zr
• 分子量: 607.837
• InChiKey: NJWIIHOHFOAXBV-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.09
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  monochlorotris[bis(trimethylsilyl)amido] zirconium 、 2,3,4,5,6-pentafluoro-N-[2-[2-[2-(2,3,4,5,6-pentafluoroanilino)ethoxy]ethoxy]ethyl]aniline 在 C₆H₅CH₃ 作用下， 以 甲苯 为溶剂， 以61%的产率得到
  参考文献：
  名称：

  Zirconium Complexes of Fluorinated Aryl Diamides

  摘要：

  The reaction of excess (ArNHLi)-N-F with (ICH2CH2OCH2)(2) affords the new diamines ((ArNHCH2CH2OCH2)-N-F)2 (1, Ar-F = C6F5; 2, Ar-F = 3,5-C6H3(CF3)(2)) in moderate yield. Direct protonolysis of Zr(CH2Ph)(n)Cl4-n (n = 2-4) or Zr[N(SiMe3)(2)](n)Cl4-n (n = 2, 3) with 1 or 2 (1 equiv) affords the zirconium complexes Zr((ArNCH2CH2OCH2)-N-F)(2)(X)(Y) (Ar-F = C6F5: 3, X = Y = Cl; 4, X = N(SiMe3)(2,) Y = Cl; 5, X = Cl, Y = CH2Ph; 6, X = Y = CH2Ph. Ar-F = 3,5-C6H3(CF3)(2): 7, X = Y = Cl; 8, X = Y = CH2Ph). The structures of 1, 4, 5, and 7 were established by X-ray crystalIography with the zirconium complexes 4, 5, and 7 all adopting a monocapped trigonal bipyramidal geometry in the solid state. However, in solution, these complexes display higher symmetry due to rapid ligand rearrangement. The silylamido complex 4 shows restricted rotation of the C6F5 rings in solution (DeltaG(double dagger) = 49 +/- 3 kJ mol(-1)). Abstraction of a benzyl group from 6 by B(C6F5)(3) affords {Zr [CH2OCH2CH2N(C6F5)](2)(CH2Ph)}(+){(PhCH2)B(C6F5)(3)} - (9) This complex shows evidence for eta (2)-benzyl coordination and does not polymerize ethylene at room temperature. Treatment of 3 with excess MAO (500 equiv) and ethylene(1 atm, 50 degreesC) affords polyethylene at a modest rate (3.2 kg mol(-1) Zr h(-1)).

  DOI：

  10.1021/om0006559
• 作为产物：
  描述：

  [(η4:η2-(C6H5CH2)2C2B9H9)2ZrCl(C4H8O)][Na(C4H8O)3] 、 lithium hexamethyldisilazane 以 甲苯 为溶剂， 以55%的产率得到monochlorotris[bis(trimethylsilyl)amido] zirconium
  参考文献：
  名称：

  取代基效应。第4个含Metallacarboranes（C的合成和结构表征6 ħ 5 CH 2）2 c ^ 2乙9 ħ 9 2 -和[ ö -C 6 ħ 4（CH 2）2 ] c ^ 2乙9 ħ 9 2 -配体

  摘要：

  碳硼烷笼碳上的取代基不仅影响4族金属离子与C 2 B 9系统的碳硼烷基之间的键合相互作用，而且还会影响所得金属配合物的反应模式。的MC1的治疗4（THF）2与1个当量的[（C 6 H ^ 5 CH 2）2 c ^ 2乙9 ħ 9 ]的Na 2（THF）X在THF中在室温下，得到双（硼烷基）络合物{ η 4：η 2 - [（C 6 H ^ 5 CH 2）2 C 2 B 9 H 9 ] 2 MCl（THF）} {Na（THF）3 }（M = Zr（1），Hf（2））。在相同的反应条件下，TiCl 4（THF）2与1当量的[（C 6 H 5 CH 2）2 C 2 B 9 H 9 ] Na 2（THF）x的相互作用导致分离出少量的TiCl 3（THF）3和B取代的两性离子化合物（C 6 H 5CH 2）2 C 2 B 9 H 9（THF）（4）。的反应1与1个当量的Li [N（森达的3）2 ]导致在更换的Na

  DOI：

  10.1021/om049629r

文献信息

• Synthesis and catalytic properties of oxalic amidinato complexes
  作者：Chi-Tien Chen、Leigh H. Rees、Andrew R. Cowley、Malcolm L. H. Green

  DOI：10.1039/b010017j

  日期：——

  The oxalic amidine compounds C6H5NC(NHtBu)–C(NHtBu)=NC6H51 and C6H5NCN(tBu)(SiMe3)}–CN(tBu)(SiMe3)}=NC6H52 are described. The compound [(C6H5N)C(NHtBu)–C(NHtBu)(NHC6H5)][Br] 3* has been isolated from the reaction between 1 and [NiBr2(DME)]. Treatment of 1 with M(NMe2)4 (M = Zr or Ti), [Ta(NEt2)2Cl3(py)] or [ZrN(SiMe3)2}3Cl] gives the bimetallic complexes [M(NMe2)3(C6H5N)C(NtBu)–]2 (M = Zr (4) or

  草酸 idine化合物C 6 H 5 N C（NH t Bu）–C（NH t Bu）= NC 6 H 5 1和C 6 H 5 N C N（t Bu）（SiMe 3）} – C N（t Bu （SiMe 3）} ＝ NC 6 H 5 2的描述。从[ 1]和[NiBr]之间的反应中分离出化合物[（C 6 H 5 N）C（NH t Bu）–C（NH t Bu）（NHC 6 H 5）] [Br] 3 *2（DME）]。的治疗1与M（NME 2） 4（M = Zr或Ti），[TA（NET 2） 2氯3（PY）]或[Zr的N（森达3） 2 } 3 CL]给出了双金属配合物[ M（NMe 2） 3（C 6 H 5 N）C（N t Bu）–] 2（M = Zr（ 4）或M = Ti（ 5））和单酰胺基络合物[Ta（NEt 2）Cl 3 （C 6 H 5 N）C（N t Bu）C（HN tBu）（NC
• Preparation, properties, and crystal structures of the monochlorotris[bis(trimethylsilyl)amido]-compounds of titanium, zirconium, and hafnium
  作者：Claudio Airoldi、Donald C. Bradley、Halina Chudzynska、Michael B. Hursthouse、K. M. Abdul Malik、Paul R. Raithby

  DOI：10.1039/dt9800002010

  日期：——

  The monomeric compounds [MClN(SiMe3)2}3](M = Ti, Zr, or Hf) have been prepared by the reaction of MCl4 with excess of Li[N(SiMe3)2]. Mass and i.r. spectra have been obtained, together with variable-temperature 1H n.m.r. spectra which shows evidence of fluxional behaviour of the bulky ligands. Molecular structures have been determined by single-crystal X-ray diffraction for the whole series. The three

  单体化合物[MCl N（SiMe 3）2 } 3 ]（M = Ti，Zr或Hf）是通过MCl 4与过量的Li [N（SiMe 3）2 ]反应制备的。获得了质谱和红外光谱，以及可变温度的1 H nmr光谱，该光谱显示了大体积配体的通量行为。对于整个系列，已经通过单晶X射线衍射确定了分子结构。这三个化合物在R 3 c空间组中具有等构结构，晶格参数（六边形设置）a = b = 18.076、18.317、18.304和Ti，Zr和Hf的c分别为17.208、17.078和17.085Å。通过重原子方法的结构分析和全矩阵最小二乘法的细化，分别基于577、1182和1195的Ti，Zr和Hf唯一数据，得出R值为0.048、0.029和0.053。根据空间效应和金属-配体键的性质讨论了结构和光谱结果。
• Substituent Effects. Synthesis and Structural Characterization of Group 4 Metallacarboranes Containing (C₆H₅CH₂)₂C₂B₉H₉²^- and [<i>o</i>-C₆H₄(CH₂)₂]C₂B₉H₉²^- Ligands
  作者：Wai-Chuen Kwong、Hoi-Shan Chan、Yong Tang、Zuowei Xie

  DOI：10.1021/om049629r

  日期：2004.8.1

  Substituents on the carborane cage carbons affect not only bonding interactions between the group 4 metal ion and the carboranyl of the C2B9 system but also the reactivity pattern of the resulting metal complexes. Treatment of MCl4(THF)2 with 1 equiv of [(C6H5CH2)2C2B9H9]Na2(THF)x in THF at room temperature gave the bis(carboranyl) complexes η4:η2-[(C6H5CH2)2C2B9H9]2MCl(THF)}Na(THF)3} (M = Zr (1)

  碳硼烷笼碳上的取代基不仅影响4族金属离子与C 2 B 9系统的碳硼烷基之间的键合相互作用，而且还会影响所得金属配合物的反应模式。的MC1的治疗4（THF）2与1个当量的[（C 6 H ^ 5 CH 2）2 c ^ 2乙9 ħ 9 ]的Na 2（THF）X在THF中在室温下，得到双（硼烷基）络合物 η 4：η 2 - [（C 6 H ^ 5 CH 2）2 C 2 B 9 H 9 ] 2 MCl（THF）} Na（THF）3 }（M = Zr（1），Hf（2））。在相同的反应条件下，TiCl 4（THF）2与1当量的[（C 6 H 5 CH 2）2 C 2 B 9 H 9 ] Na 2（THF）x的相互作用导致分离出少量的TiCl 3（THF）3和B取代的两性离子化合物（C 6 H 5CH 2）2 C 2 B 9 H 9（THF）（4）。的反应1与1个当量的Li [N（森达的3）2 ]导致在更换的Na
• Zirconium Complexes of Fluorinated Aryl Diamides
  作者：Paul E. O'Connor、Darryl J. Morrison、Sheryl Steeves、Katherine Burrage、David J. Berg

  DOI：10.1021/om0006559

  日期：2001.3.1

  The reaction of excess (ArNHLi)-N-F with (ICH2CH2OCH2)(2) affords the new diamines ((ArNHCH2CH2OCH2)-N-F)2 (1, Ar-F = C6F5; 2, Ar-F = 3,5-C6H3(CF3)(2)) in moderate yield. Direct protonolysis of Zr(CH2Ph)(n)Cl4-n (n = 2-4) or Zr[N(SiMe3)(2)](n)Cl4-n (n = 2, 3) with 1 or 2 (1 equiv) affords the zirconium complexes Zr((ArNCH2CH2OCH2)-N-F)(2)(X)(Y) (Ar-F = C6F5: 3, X = Y = Cl; 4, X = N(SiMe3)(2,) Y = Cl; 5, X = Cl, Y = CH2Ph; 6, X = Y = CH2Ph. Ar-F = 3,5-C6H3(CF3)(2): 7, X = Y = Cl; 8, X = Y = CH2Ph). The structures of 1, 4, 5, and 7 were established by X-ray crystalIography with the zirconium complexes 4, 5, and 7 all adopting a monocapped trigonal bipyramidal geometry in the solid state. However, in solution, these complexes display higher symmetry due to rapid ligand rearrangement. The silylamido complex 4 shows restricted rotation of the C6F5 rings in solution (DeltaG(double dagger) = 49 +/- 3 kJ mol(-1)). Abstraction of a benzyl group from 6 by B(C6F5)(3) affords Zr [CH2OCH2CH2N(C6F5)](2)(CH2Ph)}(+)(PhCH2)B(C6F5)(3)} - (9) This complex shows evidence for eta (2)-benzyl coordination and does not polymerize ethylene at room temperature. Treatment of 3 with excess MAO (500 equiv) and ethylene(1 atm, 50 degreesC) affords polyethylene at a modest rate (3.2 kg mol(-1) Zr h(-1)).