[CpZrCl₂{CpSiMe₂C₆H₄}]₂ | 17937-46-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [CpZrCl₂{CpSiMe₂C₆H₄}]₂
• 英文别名: Si,Si'-dichloro-Si,Si,Si',Si'-tetramethyl-Si,Si'-biphenyl-4,4'-diyl-bis-silane；Si,Si'-Dichlor-Si,Si,Si',Si'-tetramethyl-Si,Si'-biphenyl-4,4'-diyl-bis-silan；4,4'-Bis-(chlor-dimethyl-silyl)-biphenyl；Chloro-[4-[4-[chloro(dimethyl)silyl]phenyl]phenyl]-dimethylsilane
• CAS: 17937-46-1
• 化学式: C₁₆H₂₀Cl₂Si₂
• 分子量: 339.412
• InChiKey: GQLXFTOBSOJZBZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.66
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  [CpZrCl₂{CpSiMe₂C₆H₄}]₂ 、 丙炔 在 正丁基锂 作用下， 生成 [4-[4-[Dimethyl(prop-1-ynyl)silyl]phenyl]phenyl]-dimethyl-prop-1-ynylsilane
  参考文献：
  名称：

  Efficient Zirconocene-Coupling of Silicon-Substituted Diynes to Polymers and Macrocycles

  摘要：

  The zirconocene-coupling of diynes with internal silicon substituents, MeC=CMe2SiArSiMe2C=CMe (1: Ar = 1,4-C6H4; 2: Ar = 1,3-C6H4; 3: Ar = 4,4'-C6H4C6H4), generates regiospecific polymers containing zirconacyclopentadiene in the main chain (5-7). These organometallic polymers hydrolyze cleanly to butadienediyl polymers of the type [Me2SiArSiMe2CH=CMeCMe=CH](n) (11-13), and polymer 5 reacts with iodine to give the iodine-containing polymer [1,4-Me2SiC6H4SiMe2C(I)=CMeCMe=C(I)](n) (14). The organometallic polymers undergo facile and high-yield degradations to macrocycles under mild conditions (refluxing tetrahydrofuran solution). The size and shape of the resulting macrocycles depend upon the nature of the diyne spacer group. Thus, polymers 5 and 7 containing parallel diyne units convert to the trimeric macrocycles [Me2SiArSiMe2C4Me2ZrCp2](3) (15: Ar = 1,4-C6H4; 24: Ar = 4,4'-C6H4C6H4), while polymer 6 gives the dimeric macrocycle [1,3-Me2SiC6H4SiMe2C4Me2ZrCp2](2) (18). The dimeric macrocycle [Me2SiC6H4-SiMe2C6H4SiMe2C4Me2ZrCp2](2) (20) was obtained directly from the zirconocene coupling of Me2Si[(1,4-C6H4)SiMe2(C=CMe)](2) (4) by heating the reaction mixture to reflux. In. similar manner, the diyne Me2Si(C=CMe)(2) was converted in high yield to the hexameric macrocycle [Me2SiC4Me2ZrCp2](6) (22). The macrocycles 15, [1,4-Me2SiC6H4SiMe2C4Me2H2](3) (16), and 18 were characterized by single-crystal X-ray crystallography. Molecules of 15 adopt a nearly planar Cg macrocyclic structure with a cavity described by an average transannular Si ... Si distance of 13.2 Angstrom, while the hydrolyzed macrocycle 16 has a chair conformation. This conformation change results from conversion of cis diene groups in the zirconacyclopendiene fragments to trans diene groups in 16. The high-yield formation of macrocycles apparently results from the reversible nature of the alkyne-coupling reaction, which allows for a low-energy pathway to the smallest macrocycle possessing minimal ring strain.

  DOI：

  10.1021/ja973180u
• 作为产物：
  描述：

  4,4'-二溴联苯 在 magnesium 、 乙酰氯 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 生成 [CpZrCl₂{CpSiMe₂C₆H₄}]₂
  参考文献：
  名称：

  Efficient Zirconocene-Coupling of Silicon-Substituted Diynes to Polymers and Macrocycles

  摘要：

  The zirconocene-coupling of diynes with internal silicon substituents, MeC=CMe2SiArSiMe2C=CMe (1: Ar = 1,4-C6H4; 2: Ar = 1,3-C6H4; 3: Ar = 4,4'-C6H4C6H4), generates regiospecific polymers containing zirconacyclopentadiene in the main chain (5-7). These organometallic polymers hydrolyze cleanly to butadienediyl polymers of the type [Me2SiArSiMe2CH=CMeCMe=CH](n) (11-13), and polymer 5 reacts with iodine to give the iodine-containing polymer [1,4-Me2SiC6H4SiMe2C(I)=CMeCMe=C(I)](n) (14). The organometallic polymers undergo facile and high-yield degradations to macrocycles under mild conditions (refluxing tetrahydrofuran solution). The size and shape of the resulting macrocycles depend upon the nature of the diyne spacer group. Thus, polymers 5 and 7 containing parallel diyne units convert to the trimeric macrocycles [Me2SiArSiMe2C4Me2ZrCp2](3) (15: Ar = 1,4-C6H4; 24: Ar = 4,4'-C6H4C6H4), while polymer 6 gives the dimeric macrocycle [1,3-Me2SiC6H4SiMe2C4Me2ZrCp2](2) (18). The dimeric macrocycle [Me2SiC6H4-SiMe2C6H4SiMe2C4Me2ZrCp2](2) (20) was obtained directly from the zirconocene coupling of Me2Si[(1,4-C6H4)SiMe2(C=CMe)](2) (4) by heating the reaction mixture to reflux. In. similar manner, the diyne Me2Si(C=CMe)(2) was converted in high yield to the hexameric macrocycle [Me2SiC4Me2ZrCp2](6) (22). The macrocycles 15, [1,4-Me2SiC6H4SiMe2C4Me2H2](3) (16), and 18 were characterized by single-crystal X-ray crystallography. Molecules of 15 adopt a nearly planar Cg macrocyclic structure with a cavity described by an average transannular Si ... Si distance of 13.2 Angstrom, while the hydrolyzed macrocycle 16 has a chair conformation. This conformation change results from conversion of cis diene groups in the zirconacyclopendiene fragments to trans diene groups in 16. The high-yield formation of macrocycles apparently results from the reversible nature of the alkyne-coupling reaction, which allows for a low-energy pathway to the smallest macrocycle possessing minimal ring strain.

  DOI：

  10.1021/ja973180u

文献信息

• Zirconocene Complexes as Catalysts for the Cycloaddition of CO ₂ to Propylene Oxide
  作者：So Han Kim、Duseong Ahn、Yi Young Kang、Min Kim、Ki‐Soo Lee、Junseong Lee、Myung Hwan Park、Youngjo Kim

  DOI：10.1002/ejic.201402782

  日期：2014.10

  Six zirconocene derivatives were systematically designed; one of the cyclopentadienyl (Cp) ligands of zirconocene dichloride [Cp2ZrCl2] was silylated and this group was then incrementally increased in size; furthermore, one derivative with a 4,4′-disilylbiphenyl bridge between the two zirconocene fragments was prepared. One zirconium complex was characterized by single-crystal X-ray analysis. All zirconium

  系统设计了六种二茂锆衍生物；二氯化锆 [Cp2ZrCl2] 的环戊二烯基 (Cp) 配体之一被甲硅烷基化，然后该基团的大小逐渐增加；此外，制备了一种在两个二茂锆片段之间具有 4,4'-二甲硅烷基联苯桥的衍生物。一种锆配合物通过单晶 X 射线分析表征。所有锆配合物都是将 CO2 环加成到环氧丙烷的有效催化剂。含有连接到 SiMe2 基团的联苯基的两种配合物显示出比其他配合物更高的活性。此外，在所有报道的锆配合物中，含有联亚苯基双（二甲基甲硅烷基）桥的双核配合物显示出最高的活性。此外，
• Notes - Aromatic Organosilicon Compounds
  作者：Gerald Baum

  DOI：10.1021/jo01097a602

  日期：1958.3
• Efficient Zirconocene-Coupling of Silicon-Substituted Diynes to Polymers and Macrocycles
  作者：Shane S. H. Mao、Feng-Quan Liu、T. Don Tilley

  DOI：10.1021/ja973180u

  日期：1998.2.1

  The zirconocene-coupling of diynes with internal silicon substituents, MeC=CMe2SiArSiMe2C=CMe (1: Ar = 1,4-C6H4; 2: Ar = 1,3-C6H4; 3: Ar = 4,4'-C6H4C6H4), generates regiospecific polymers containing zirconacyclopentadiene in the main chain (5-7). These organometallic polymers hydrolyze cleanly to butadienediyl polymers of the type [Me2SiArSiMe2CH=CMeCMe=CH](n) (11-13), and polymer 5 reacts with iodine to give the iodine-containing polymer [1,4-Me2SiC6H4SiMe2C(I)=CMeCMe=C(I)](n) (14). The organometallic polymers undergo facile and high-yield degradations to macrocycles under mild conditions (refluxing tetrahydrofuran solution). The size and shape of the resulting macrocycles depend upon the nature of the diyne spacer group. Thus, polymers 5 and 7 containing parallel diyne units convert to the trimeric macrocycles [Me2SiArSiMe2C4Me2ZrCp2](3) (15: Ar = 1,4-C6H4; 24: Ar = 4,4'-C6H4C6H4), while polymer 6 gives the dimeric macrocycle [1,3-Me2SiC6H4SiMe2C4Me2ZrCp2](2) (18). The dimeric macrocycle [Me2SiC6H4-SiMe2C6H4SiMe2C4Me2ZrCp2](2) (20) was obtained directly from the zirconocene coupling of Me2Si[(1,4-C6H4)SiMe2(C=CMe)](2) (4) by heating the reaction mixture to reflux. In. similar manner, the diyne Me2Si(C=CMe)(2) was converted in high yield to the hexameric macrocycle [Me2SiC4Me2ZrCp2](6) (22). The macrocycles 15, [1,4-Me2SiC6H4SiMe2C4Me2H2](3) (16), and 18 were characterized by single-crystal X-ray crystallography. Molecules of 15 adopt a nearly planar Cg macrocyclic structure with a cavity described by an average transannular Si ... Si distance of 13.2 Angstrom, while the hydrolyzed macrocycle 16 has a chair conformation. This conformation change results from conversion of cis diene groups in the zirconacyclopendiene fragments to trans diene groups in 16. The high-yield formation of macrocycles apparently results from the reversible nature of the alkyne-coupling reaction, which allows for a low-energy pathway to the smallest macrocycle possessing minimal ring strain.