bis[(μ-dimethylsilyl)(η5-cyclopentadienyl)]dichlorozirconium | 154675-56-6

• 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: bis[(μ-dimethylsilyl)(η5-cyclopentadienyl)]dichlorozirconium
• 英文别名: ZrCl2(bis(1,1',2,2'-dimethylsilanodiyl-)η(5)-dicyclopentadienyl)；ZrCl2[μ-((SiMe2)2(η(5)-C5H3)2)]；[ZrCl2((η(5)-C5H3)2[Si(CH3)2]2)]；Zr[(SiMe2)2(η(5)-C5H5)2]Cl2；(1,1'-dimethylsilylene)(2,2'-dimethylsilylene)bis(cyclopentadienyl)zirconium dichloride；[(1,1',2,2'-(CH3)2Si)2(C5H3)2]ZrCl2
• CAS: 154675-56-6
• 化学式: C₁₄H₁₈Cl₂Si₂Zr
• 分子量: 404.598
• InChiKey: JJMWBXRNYKIFCS-UHFFFAOYSA-L

计算性质

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

• 作为反应物：
  描述：

  bis[(μ-dimethylsilyl)(η5-cyclopentadienyl)]dichlorozirconium 在 Na/Hg 作用下， 以 甲苯 为溶剂， 以70%的产率得到[Zr(bis(1,1',2,2'-dimethylsilanodiyl)-η(5)-dicyclopentadienyl)(μ-Cl)]2
  参考文献：
  名称：

  二环戊二烯基钛和锆的复合物与双桥接双（dimethylsilanodiyl）二环戊二烯基[（ME 2 Si）的2（η 5 -C 5 H ^ 3）2 ] 2-配体：X射线的钛[Ti {（森达分子结构2）2（η 5 -C 5 H ^ 3）2 }我2 ] 1

  摘要：

  所述双桥联双反应（1,1'，2,2'- dimethylsilanodiyl） - η 5 -dicyclopentadienyl钛和锆的复合物与水，得到μ氧代衍生物。将一当量的M'R（M'= MgCl，R = CH 3，CH 2 SiMe 3； M'= Li，R = CH 2 CME 2 Ph）加到甲苯或二氯乙烷的乙醚溶液中，得到氯代烷基衍生物[ μ{（森达2）2（η 5 -C 5 H ^ 3）2 } CIR] 。化合物3和4与[CPh如[ NMR ]所示，在-78℃下，在CD 2 Cl 2中的3 ] [B（C 6 F 5）4 ]产生阳离子种类。钛（III）和锆（III）serivatives [M {（森达2）2（η 5 -C 5 H ^ 3）2 }（μ -Cl）2（M =的Ti（12），锆（13））是通过用一当量的钠汞齐还原1 amd 2得到。钛[Ti {（森达的透视分子结构2）2（η

  DOI：

  10.1016/s0022-328x(96)06569-2
• 作为产物：
  描述：

  以 二氯甲烷-D2 为溶剂， 以>99的产率得到bis[(μ-dimethylsilyl)(η5-cyclopentadienyl)]dichlorozirconium
  参考文献：
  名称：

  乙烯基和炔基锆络合物与二氢-[1,1'，2,2'-双（二甲基硅烷二基）二环戊二烯基]配体的反应性

  摘要：

  的氯乙基乙烯化和二氯锆配合物[Zr的（CPSI 2 CP）CLX]（CPSI 2 CP = 1,1'，2,2' - （森达2）2（η 5 -C 5 H ^ 3）2 ; X =的Et，Cl）的用Mg（CHCH的一个或二当量2）氯，得到新zirconacyclopentane [锆（CPSI 2 CP）{η 2 -CH 2 （CH 2）2 CH 2 }]和（ η 4 -丁二烯）合锆[Zr的（CPSI 2 CP）{η 4-（丁二烯）}]配合物。PhCCPh的甲苯溶液，以得到zirconacyclopentadiene衍生物zirconacyclopentane化合物的加成中，[Zr（CPSI 2 CP）{η 2 - （CPhCPhCPhCPh）}]。氯乙基锆配合物与LiCCPh的反应得到炔基化合物[Zr（CpSi 2 Cp）Et（CCPh）]与CN（2,6-Me 2 C 6 H

  DOI：

  10.1016/s0022-328x(99)00633-6

文献信息

• Cano, Ana; Cuenca, Tomás; Gómez-Sal, Pilar, Organometallics, 1994, vol. 13, # 5, p. 1688 - 1694
  作者：Cano, Ana、Cuenca, Tomás、Gómez-Sal, Pilar、Royo, Beatriz、Royo, Pascual

  DOI：——

  日期：——
• Cationic Alkylaluminum-Complexed Zirconocene Hydrides: NMR-Spectroscopic Identification, Crystallographic Structure Determination, and Interconversion with Other Zirconocene Cations
  作者：Steven M. Baldwin、John E. Bercaw、Lawrence M. Henling、Michael W. Day、Hans H. Brintzinger

  DOI：10.1021/ja1050428

  日期：2011.2.16

  The ansa-zirconocene complex rac-Me2Si(1-indenyl)(2)-ZrCl2 ((SBI)ZrCl2) reacts with diisobutylaluminum hydride and trityl tetrakis(perfluorophenyl)borate in hydrocarbon solutions to give the cation [(SBI)Zr(mu-H)(3)((AlBu2)-Bu-i)(2)](+), the identity of which is derived from NMR data and supported by a crystallographic structure determination. Analogous reactions proceed with many other zirconocene dichloride complexes. [(SBI)Zr(mu-H)(3)((AlBu2)-Bu-i)(2)](+) reacts reversibly with (ClAlBu2)-Bu-i to give the dichloro-bridged cation [(SBI)Zr(mu-Cl)(2)(AlBu2)-Bu-i](+). Reaction with AIMe(3) first leads to mixed-alkyl species [(SBI)Zr(mu-H)(3)(AIMe(x)(i)Bu(2-x))(2)](+) by exchange of alkyl groups between aluminum centers. At higher AlMe3/Zr ratios, [(SBI)Zr(mu-Me)(2)AlMe2](+), a constituent of methylalumoxane-activated catalyst systems, is formed in an equilibrium, in which the hydride cation [(SBI)Zr(mu-H)(3)(AIR(2))(2)](+) strongly predominates at comparable HAI(i)Bu(2) and AlMe3 concentrations, thus implicating the presence of this hydride cation in olefin polymerization catalyst systems.
• Insertion of isocyanides into zirconium-alkyl bonds of di-ansa-zirconocene complexes. X-ray molecular structure of Zr{(SiMe2)2(η5−C5H3)2}Cl{η2−C(i−Pr)N(2,6-Me2C6H3)
  作者：Antonio M. Barriola、Ana M. Cano、Tomás Cuenca、Francisco J. Fernández、Pilar Gómez-Sal、Antonio Manzanero、Pascual Royo

  DOI：10.1016/s0022-328x(97)00155-1

  日期：1997.9

  New dicyclopentadienyl iminoacyl zirconium complexes have been prepared and characterized by NMR spectroscopy. The reaction of [Zr(SiMe2)(2)(eta(5)-C5H3)(2)}Me-2] with CNR (R = 2,6-Me2C6H3, t-Bu) yields [Zr(SiMe2)(2)(eta(5)-C5H3)(2)}Me(eta(2)-CMeNR)] (R = 2,6-Me2C6H3, t-Bu), which reacts with a stoichiometric amount of water to give the mu-oxo dimers [Zr(SiMe2)(2)(eta(5)-C5H3)(2)}(eta(2)-CMeNR)](2)(mu-O) (R = 2,6-Me2C6H3, t-Bu). The chloro neophyl complex [Zr(SiMe2)(2)(eta(5)-C5H3)(2)}Cl(CH2CMe2Ph)] and other beta-hydrogen containing zirconium chloro alkyls [Zr(SiMe2)(2)(eta(5)-C5H3)(2)}ClR] (R = Et, n-Pr, i-Pr) react with CN(2,6-Me2C6H3) to yield the related chloro iminoacyl complexes [Zr(SiMe2)(2)(eta(5)-C5H3)(2)}Cleta(2)-CRN(2,6-Me2C6H3)}] (R = Et, n-Pr, i-Pr), whereas no reaction was observed when CN(t-Bu) was used. All the new iminoacyl complexes were characterized by H-1 and C-13 NMR spectroscopy and the X-ray molecular structure of [Zr(SiMe2)(2)(eta(5)-C5H3)(2)}Cleta(2)-C(i-Pr)N(2,6-Me2C6H3)}] was studied by diffraction methods to prove the expected 'inside' coordination of the iminoacyl nitrogen atom. (C) 1997 Elsevier Science S.A.
• β-Hydrogen-Containing Zirconium Alkyls with the Doubly-Bridged Bis(dimethylsilanediyl)dicyclopentadienyl Ligand. X-ray Molecular Structures of [Zr{(SiMe₂)₂(η⁵-C₅H₃)₂}ClEt] and [Zr{(SiMe₂)₂(η⁵-C₅H₃)₂}Et]₂(μ-CH₂CH₂)
  作者：Francisco J. Fernández、Pilar Gómez-Sal、Antonio Manzanero、Pascual Royo、Heiko Jacobsen、Heinz Berke

  DOI：10.1021/om9610509

  日期：1997.4.1

  Alkylation of [Zr(CpSi2Cp)Cl-2] (CpSi2Cp = (eta(5)-C5H3)(2)[Si(CH3)(2)](2) with 1 equiv of RMgCl in THF at 10 degrees C gave the monoalkylated complexes [Zr(CpSi2Cp)ClR] (R = Et, n-Pr, i-Pr) in 80% yield, the isopropyl complex isomerizing to the n-propyl derivative above 10 degrees C. Addition of a second equivalent or an excess amount of the akylating agent resulted in the formation of the dialkyl compounds [Zr(CpSi2Cp)R-2] (R = Et, n-Pr). Hydrolysis of [Zr(CpSi2Cp)ClR] led to the mu-oxo dinuclear complex [Zr(CpSi2Cp)Cl}(2)(mu-O)]. Thermal decomposition of THF solutions of [Zr(CpSi2Cp)ClR] takes place with the evolution of an equimolar amount of alkane and alkene and the formation of [Zr(CpSi2Cp)Cl-2] and an unidentified residue. Formation of [Zr(CpSi2Cp)Et-2] is always accompanied by decomposition with the evolution of ethane to give [Zr(CpSi2Cp)Et}(2)(mu-CH2=CH2)] in 70% yield. A similar behavior was observed for [Zr(CpSi2Cp)(n-Pr)(2)]. All of the compounds were characterized by elemental analysis and NMR spectroscopy, and the molecular structures of [Zr(CpSi2Cp)ClEt] and [Zr(CpSi2Cp)Et}(2)(mu-CH2=CH2)] were studied by X-ray diffraction methods. Density functional calculations on the model compound [ZrCp2Me}(2)(mu-CH2=CH2)] satisfactorily reproduce d(C-C) = 1.482, d1(Zr-C) = 2.327 Angstrom, and d2(Zr-C) = 2.506 Angstrom, the geometry found experimentally.
• Ring-Opening Polymerization Behavior of <i>ansa</i>- and Spirocyclic <i>ansa</i>-Zirconocene Complexes
  作者：Timothy J. Peckham、Paul Nguyen、Sara C. Bourke、Qinyan Wang、Daryll G. Harrison、Peter Zoricak、Charles Russell、Louise M. Liable-Sands、Arnold L. Rheingold、Alan J. Lough、Ian Manners

  DOI：10.1021/om001023p

  日期：2001.7.1

  Attempts to develop a ring-opening polymerization (ROP) approach to polymeric zirconocene complexes are reported. A new silicon-bridged [1][1] zirconocenophane, (SiMe2)(2)(eta (5)-C5H3)(2)Zr(NEt2)(2) (3a), was synthesized by reaction of Zr(NEt2)(4) with (C5H4)(2)(SiMe2)(2) (4) Single-crystal X-ray diffraction revealed a highly tilted structure with an angle of 73.1(4)degrees, a significant increase over the untethered compound (eta (5)-MeC5H4)(2)ZrCl2 (2), which possesses a tilt angle of 54.2 degrees. This and the related compounds (SiMe2)(eta (5)-C5H4)(2)MCl2 (1a, M = Ti; Ib, M = Zr) and (SiMe2)(2)(eta (5)-C5H3)(2)ZrCl2 (3b) were tested for transition-metal catalyzed ROP behavior in the presence of Pt(0) catalysts but were found to be inactive. The novel spirocyclic silacyclobutane-bridged monomer (CH2)(3)Si(eta (5)-C5H4)(2)ZrCl2 (7b) was prepared via a "fly trap" amine elimination reaction between cyclotrimethylenedicyclopentadienylsilane (8) and Zr(NMe2)(4); this initially yielded (CH2)(3)Si(eta (5)-C5H4)(2)Zr(NMe2)(2) (7a), which was converted to 7b by reaction with a slight excess of Me3SiCl. 7a and 7b were characterized by Si-29, C-13, and H-1 NMR spectroscopy and mass spectrometry as well as single-crystal X-ray diffraction. Both showed moderate tilt angles (61.7(2)degrees and 59.69(7)degrees, respectively) as well as highly strained silacyclobutane rings with C-Si-C bond angles of 79.7(2)degrees and 80.64(10)4 respectively. Transition-metal-catalyzed ROP of 7b led to the formation of the polycarbosilane [(CH2)(3)Si(eta (5)-C5H4)(2)ZrCl2](n) (10). Both the soluble and insoluble fractions of 10 were characterized by CP-MAS Si-29 and C-13 NMR, and the soluble, oligomeric fraction was further characterized by solution Si-29, C-13,and H-1 NMR. Complexes 7a, 7b, and polyzirconocene 10 were found to exhibit moderate activity as ethylene polymerization catalysts.