二(二(三甲基硅烷基)氨基)-二氯-锆 | 70969-28-7

• 物质功能分类: 化学试剂 - 有机试剂 - 硅烷
• 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
• 中文名称: 二(二(三甲基硅烷基)氨基)-二氯-锆
• 英文名称: dichlorobis[bis(trimethylsilyl)amido]zirconium
• 英文别名: [(Me3Si)2N]2ZrCl2；bis(trimethylsilyl)azanide;zirconium(4+);dichloride
• CAS: 70969-28-7
• 化学式: C₁₂H₃₆Cl₂N₂Si₄Zr
• 分子量: 482.903
• InChiKey: YTWXEUAUHRSZID-UHFFFAOYSA-L

物化性质

• 熔点：
  50°C

计算性质

• 辛醇/水分配系数(LogP)：
  7.44
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• TSCA：
  No

反应信息

• 作为反应物：
  描述：

  二(二(三甲基硅烷基)氨基)-二氯-锆 以 乙醚 、 正戊烷 为溶剂， 生成
  参考文献：
  名称：

  Planalp, Roy P.; Andersen, Richard A.; Zalkin, Allan, Organometallics, 1983, vol. 2, # 1, p. 16 - 20

  摘要：

  DOI：
• 作为产物：
  描述：

  sodium hexamethyldisilazane 、 氯化锆(IV) 以 not given 为溶剂， 生成 二(二(三甲基硅烷基)氨基)-二氯-锆
  参考文献：
  名称：

  Zirconium Complexes of a Cross-Bridged Cyclam

  摘要：

  The acid-base reaction of tetrabenzylzirconium with 1,4,8,11-tetraazabicyclo[6.6.2]-hexadecane (H-2(CBC), 1) produces (CBC)Zr(CH2Ph)(2), 2. Similarly, reaction of 2 with phenols yields (CBC)Zr(CH2Ph)(O-2,6-C6H3Bu2t), 3, and (CBC)Zr(O-2,6-C6H3Me2)(2), 5. Prolonged heating of 3 leads to the metalated product (CBC)Zr[kappa(2)(C,O)-OC6H3(6-Bu-t)(2-CMe2CH2)], 4. Reaction of ZrCl2[N(SiMe3)(2)](2) with H-2(CBC) leads to (CBC)ZrCl2, 6, which subsequently affords (CBC)Zr(X)(Y) by salt metathesis (7, X = Cl, Y = N(SiMe3)2; 8, X = Y = CH3; 9, X = Y = CH2Si(CH3)(3)). Compounds 3 and 7 show restricted rotation about the Zr-O and Zr-N bonds, respectively, on the NMR time scale. For 3, the energy of activation for this process was determined to be 69 +/- 1 kJ/mol. Neither 6 nor 8 shows ethylene polymerization activity when treated with 500 equiv of MAO. Reaction of 6 with 2 equiv of n-BuLi in the presence of excess diphenylacetylene leads to the zirconacyclopentadiene 10, (CBC)Zr(C4Ph4). The structures of 5, 9, and 10 have been determined by X-ray crystallography, and all three display distorted octahedral geometry.

  DOI：

  10.1021/om049469j

文献信息

• Oxo-Bridged Bis(group 4 metal unsymmetric phosphonium-stabilized carbene) Complexes
  作者：Jia-Yi Guo、Yuk-Chi Chan、Yongxin Li、Rakesh Ganguly、Cheuk-Wai So

  DOI：10.1021/om5012962

  日期：2015.4.13

  The synthesis and reactivity of oxo-bridged bis(group 4 metal unsymmetric phosphonium-stabilized carbene) complexes are described. The reaction of [CH2RNRS] (1; RN = PPh2NSiMe3, RS = PPh2S) with 1 equiv of [M(NMe2)4] (M = Zr, Hf) afforded the group 4 metal unsymmetric phosphonium-stabilized carbene complexes [M(NMe2)2(CRNRS)] (M = Zr (4), Hf (5)). Their reactions with water in toluene afforded the

  描述了羰基桥联的双（4族金属非对称phospho稳定的卡宾）配合物的合成和反应活性。[CH 2 R N R S ]（1； R N = PPh 2 NSiMe 3，R S = PPh 2 S）与1当量的[M（NMe 2）4 ]（M = Zr，Hf）反应得到第4组金属非对称phospho稳定的卡宾配合物[M（NMe 2）2（CR N R S）]（M = Zr（4），Hf（5））。他们与水在甲苯中的反应提供了羰基桥联的衍生物O [M（NMe 2）（CR N R S）] 2（M = Zr（6），Hf（7））。化合物6与AdNCO进行插入反应以形成O [Zr OC（NMe 2）NAd}（CR N R S）] 2（8； Ad ＝金刚烷基）。化合物4 - 8由NMR光谱和X-射线晶体学进行了表征。
• Dibenzylzirconium Complexes of Chelating Aminodiolates. Synthesis, Structural Studies, Thermal Stability, and Insertion Chemistry
  作者：Pengcheng Shao、Roland A. L. Gendron、David J. Berg、Gordon W. Bushnell

  DOI：10.1021/om9907324

  日期：2000.2.1

  the complexes. Complexes bearing tert-butyl groups (2c,d) readily undergo thermal decomposition by elimination of isobutene. Thermal ortho metalation of the chiral complex Zr[((S)-PhC(H)Me)N(CH2CH2C(O)Me2][CH2Ph]2 (2e) affords the chiral metallacycle Zr[NCH2CH2C(O)Me2}2((S)-2-C6H4C(H)Me}][CH2Ph] (7), which has been structurally characterized. Reaction of 7 with 1 equiv of aryl aldehyde (ArC(O)H; Ar

  Aminodiolate配体，RN（CH 2 CH 2 C（O）R ' 2）2（1A - ë），允许的可溶性隔离，单体锆二烷基配合物，[RN（CH 2 CH 2 C（O）R' 2）2 ] ZRR”' 2（2A - ë，5，6）。的fluxional行为和这些复合物的热稳定性是强烈地依赖于取代基中的氮中心的性质，以更小的取代基（R =甲基;图2a，b，5，6）提高配合物的刚性和热稳定性。带有叔丁基的络合物（2c，d）易于通过消除异丁烯进行热分解。手性配合物Zr [（（S）-PhC（H）Me）N（CH 2 CH 2 C（O）Me 2 ] [CH 2 Ph] 2（2e）的热邻位金属化得到手性金属环Zr [N CH 2 CH 2 C（O）Me 2 } 2 （（S）-2-C 6 H 4 C（H）Me}] [CH 2 Ph]（7），具有结构特点。的反应7与1个当量芳基醛（ARC（O）H; Ar为pH值，β
• Alkene polymerization by a cationic zirconium diamide complex formed by ligand cyclometallation
  作者：Andrew D. Horton、Jan de With

  DOI：10.1039/cc9960001375

  日期：——

  Reaction of (Me3Si)2N}2Zr(CH2Ph)2 1 with B(C6F5)3 gives a cationic benzyl complex, which at –25 °C, expels toluene to afford (Me3Si)2N}[graphic omitted]SiMe3)ηn-PhCH2-B(C6F5)3}2; strong anion coordination to zirconium in cyclometallation product 2 suppresses alkene polymerization, whereas the analogous cationic NMe2Ph adduct 3, formed by protonolysis of 1, polymerizes both ethene and propene.

  反应物 (Me3Si)2N}2Zr(CH2Ph)2 1 与 B(C6F5)3 反应生成一个阳离子苄基配合物，在 -25 °C 下，该配合物会排除甲苯，生成 (Me3Si)2N}[省略图]SiMe3)ηn-PhCH2-B(C6F5)3}2；在环金属化产物 2 中，强阴离子对锆的配位抑制了烯烃聚合，而通过 1 的质子解离形成的类似阳离子 NMe2Ph 配合物 3，则聚合了乙烯和丙烯。
• Biphenolate Phosphine Complexes of Group 4 Metals
  作者：Lan-Chang Liang、Yu-Ning Chang、Hon Man Lee

  DOI：10.1021/ic062314e

  日期：2007.4.1

  The preparation and structural characterization of a series of group 4 complexes supported by 2,2'-phenylphosphinobis(4,6-di-tert-butylphenolate) ([OPO](2-)) are described. The reaction of either H-2[OPO] with Ti(OR)(4) (R = Et, Pr-i) or Li-2[OPO] with TiCl4(THF)(2) produced yellowish-orange crystals of Ti[OPO](2), regardless of the stoichiometry of the starting materials employed. Comproportionation of the bis-ligand complex Ti[OPO](2) with 1 equiv of TiCl4(THF)(2) led to the formation of [OPO]TiCl2(THF) as brownish-red crystals. Surprisingly, treatment of H-2[OPO] with [(Me3Si)(2)N](2)MCl2 (M = Zr, Hf), irrespective of the molar ratio, generated colorless crystals of the corresponding bis-ligand complex [OPO](2)M(OH2) as an aqua adduct. The solution and solid-state structures of these group 4 complexes were all characterized by multinuclear NMR spectroscopy and X-ray crystallography, respectively.
• 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)).