[(TiCl2)2(μ-((η5-C5Me4SiMeO)2(μ-O)))] | 1073488-47-7

• 英文名称: [(TiCl2)2(μ-((η5-C5Me4SiMeO)2(μ-O)))]
• CAS: 1073488-47-7
• 化学式: C₂₀H₃₀Cl₄O₃Si₂Ti₂
• 分子量: 612.199
• InChiKey: IESZIHAKGAGSMY-GVGYRTLJSA-J

计算性质

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

  tris(pentafluorophenyl)aluminum*(toluene)0.5 、 [(TiCl2)2(μ-((η5-C5Me4SiMeO)2(μ-O)))] 以 甲苯 为溶剂， 以85%的产率得到[(TiCl2)2(μ-((η5-C5Me4SiMeO)2(μ-OAl(C6F5)3)))]
  参考文献：
  名称：

  单核和双核环戊二烯基硅氧烷复合物：合成，反应性和催化聚合应用

  摘要：

  的（二氯）环戊二烯基钛化合物的水解钛[Ti（η 5 -C 5我4 SiMeCl 2）氯3 ]，获得本metallasiloxane双核配合物[（的TiCl 2）2（μ - {（η 5 -C 5我4 SIMEO）2（μ-O）}）]（1a）。加入4当量RMgCl（R = Me中，BZ）的至1A，得到相应的四烷基二钛衍生物[（TIR 2）2（μ - {（η 5 -C 5我4 SIMEO）2（μ-O）}）] （R =我1b，Bz 1c）。苄基化合物1c与E（C 6 F 5）3（E = B，Al）和[Ph 3 C] [B（C 6 F 5）4 ]反应生成桥连二钛化合物[（TiBz）2（μ - {（η 5 -C 5我4 SIMEO）2（μ-O）}）（μ-X）] [Q]（Q = BZB（C 6 ˚F 5）3 ; X = Br的，2BR ;氯，2CL ; F，2F ; Q = BzAl（C 6 F 5）3;

  DOI：

  10.1021/om800492e
• 作为产物：
  描述：

  [Ti(η5-C5Me4SiMeCl2)Cl3] 、 水 以 乙醚 、 水 为溶剂， 以90%的产率得到[(TiCl2)2(μ-((η5-C5Me4SiMeO)2(μ-O)))]
  参考文献：
  名称：

  单核和双核环戊二烯基硅氧烷复合物：合成，反应性和催化聚合应用

  摘要：

  的（二氯）环戊二烯基钛化合物的水解钛[Ti（η 5 -C 5我4 SiMeCl 2）氯3 ]，获得本metallasiloxane双核配合物[（的TiCl 2）2（μ - {（η 5 -C 5我4 SIMEO）2（μ-O）}）]（1a）。加入4当量RMgCl（R = Me中，BZ）的至1A，得到相应的四烷基二钛衍生物[（TIR 2）2（μ - {（η 5 -C 5我4 SIMEO）2（μ-O）}）] （R =我1b，Bz 1c）。苄基化合物1c与E（C 6 F 5）3（E = B，Al）和[Ph 3 C] [B（C 6 F 5）4 ]反应生成桥连二钛化合物[（TiBz）2（μ - {（η 5 -C 5我4 SIMEO）2（μ-O）}）（μ-X）] [Q]（Q = BZB（C 6 ˚F 5）3 ; X = Br的，2BR ;氯，2CL ; F，2F ; Q = BzAl（C 6 F 5）3;

  DOI：

  10.1021/om800492e

文献信息

• Dinuclear dialkoxo-bridged cyclopentadienylsiloxo titanium complexes
  作者：Lorena Postigo、Javier Sánchez-Nieves、Pascual Royo、Marta E. G. Mosquera

  DOI：10.1039/b820092k

  日期：——

  The dinuclear dialkoxo-bridged complexes [(TiCl)2(μ-O2L)(μ-(η5-C5Me4SiMeO)2(μ-O)})] (O2L = 1,2-O2C2H41a, 1,2-O2C6H41b, 1,2-(OCH2)2C6H41c, O2SiPh21d) were obtained by reaction of [(TiCl2)2(μ-(η5-C5Me4SiMeO)2(μ-O)})] (A) with the corresponding dilithium salt (1a) or diol (1b, 1c, 1d). Alkylation of 1a and 1b with ClRMg afforded [(TiR)2(μ-O2L)(μ-(η5-C5Me4SiMeO)2(μ-O)})] (O2L = 1,2-O2C2H4, R = Me 2a, Bz 3a; O2L = 1,2-O2C6H4, R = Me 2b, Bz 3b). Addition of four equiv. of LiOiPr to A afforded [Ti(OiPr)2}2(μ-(η5-C5Me4SiMeO)2(μ-O)})] (4). Reaction of 1a with Al(C6F5)3 produced the elimination of the dialkoxo ligand to give [TiCl(C6F5)}2(μ-(η5-C5Me4SiMeO)2(μ-O)})] (5), whereas the same reaction of 1b with Al(C6F5)3 produced the oxo-alane adduct [(TiCl)2(μ-O2L)(μ-(η5-C5Me4SiMeO)2(μ-O·AlC6F5}3)})] (O2L = 1,2-O2C6H46) which was further transformed to give a mixture of 5 and [(TiCl)Ti(C6F5)}(μ-O2L)(μ-(η5-C5Me4SiMeO)2(μ-O)})] (O2L = 1,2-O2C6H47). One benzyl group of complexes 3 was abstracted with E(C6F5)3 (E = B, Al) to give the monoionic compounds [Ti(TiBz)(μ-O2L)(μ-(η5-C5Me4SiMeO)2(μ-O)})][BzE(C6F5)3] (O2L = 1,2-O2C2H4, E = B 8B, Al 8Al; O2L = 1,2-O2C6H4, E = B 9B), although 8Al was unstable in CD2Cl2 evolving to a mixture of compounds where [(TiBz)2(μ-Cl)(μ-(η5-C5Me4SiMeO)2(μ-O)})][BzAl(C6F5)3] (10) was identified, and compound 9B was also unstable at ambient temperature. Polymerization of ε-caprolactone was only achieved with the tetraalkoxo compound 4. All of these complexes were characterized by NMR spectroscopy and 1a, 1b and 7 by X-ray diffraction studies.

  双核二酮桥配合物[(TiCl)2(μ-O2L)(μ-(η5-C5Me4SiMeO)2(μ-O)})]（O2L = 1,2-O2C2H41a，1,2-O2C6H41b，1,2-(OCH2)2C6H41c、O2SiPh21d）是通过[(TiCl2)2(μ-(η5-C5Me4SiMeO)2(μ-O)}]（A）与相应的二锂盐（1a）或二元醇（1b、1c、1d）反应得到的。）用 ClRMg 烷基化 1a 和 1b，得到[(TiR)2(μ-O2L)(μ-(η5-C5Me4SiMeO)2(μ-O)})]（O2L = 1,2-O2C2H4，R = Me 2a，Bz 3a；O2L = 1,2-O2C6H4，R = Me 2b，Bz 3b）。在 A 中加入四当量的 LiOiPr，得到 [Ti(OiPr)2}2(μ-(η5-C5Me4SiMeO)2(μ-O)})] (4)。1a 与 Al(C6F5)3 反应后，二酮氧配体被消除，得到 [TiCl( )}2(μ-(η5-C5Me4SiMeO)2(μ-O)})] (5)、而 1b 与 Al( )3 的相同反应生成了氧代丙烷加合物[(TiCl)2(μ-O2L)(μ-(η5-C5Me4SiMeO)2(μ-O-Al }3)})]（O2L = 1、2-O2C6H46）的混合物，进一步转化得到 5 和[(TiCl)Ti( )}(μ-O2L)(μ-(η5-C5Me4SiMeO)2(μ-O)})]（O2L = 1,2-O2C6H47）的混合物。配合物 3 的一个苄基被 E( )3 （E = B、Al）抽取，得到单离子化合物 [Ti(TiBz)(μ-O2L)(μ-(η5-C5Me4SiMeO)2(μ-O)})][BzE( )3] （O2L = 1,2-O2C2H4，E = B 8B，Al 8Al；O2L=1,2-O2C6H4，E=B 9B），但 8Al 在 CD2Cl2 中不稳定，会演化成一种化合物混合物，其中 [(TiBz)2(μ-Cl)(μ-(η5-C5Me4SiMeO)2(μ-O)})][BzAl( )3]（10）已经确定，化合物 9B 在环境温度下也不稳定。只有四烷氧基化合物 4 实现了 ε-己内酯的聚合。所有这些复合物都通过核磁共振光谱进行了表征，1a、1b 和 7 则通过 X 射线衍射研究进行了表征。
• Dinuclear Dicyclopentadienyl Titanium Complexes with Bridging Cyclopentadienylsiloxo Ligands
  作者：Lorena Postigo、Luca Bellarosa、Javier Sánchez-Nieves、Pascual Royo、Agustí Lledós、Marta E. G. Mosquera

  DOI：10.1021/om900938m

  日期：2010.2.8

  Addition of 1 equiv of TlCp to compound [(TiCl2)(2)(mu-(eta(5)-C5Me4SiMeO)(2)(mu-O)})] (A) at 80 degrees C gave it mixture with different molar ratios of the two possible isomers of [(TiClCp)(TiCl2)(mu-(eta(5)- C5Me4SiMeO)(2)(mu-O)})] (1). Reaction of compound A with 2 equiv of TlCp at 80 degrees C afforded [(TiClCP)(2)(mu-(eta(5)-C5Me4SiMeO)(2)(mu-O)})] (2as) as the unique reaction product. Each Cp ligand of 2as is located in different positions anti and syn with respect to the Si-O-Si bridge. However, a mixture of two isomers of [(TiClCp)(2)(mu-(eta(5)-C5Me4SiMeO)(2)(mu-O)})], 2as ( > 95% by NMR) and 2aa ( <5% by NMR), wits obtained when the reaction was carried out at 60 degrees C; the two Cp ligands of 2aa were located at anti positions. Alkylation of isomer 2as with LiMe gave it mixture of the three possible isomers [(TiMeCp)(2)(mu-(eta(5)-C5Me4SiMeO)(2)(mu-O)})] (3as, 3aa, 3ss). The proportion of each was dependent on the reaction temperature. Isomer 2as reacted with Lewis acids E(C6F5)(3) (E = B, Al) and with Li[B(C6F5)(4)] to give the chloro-bridged dititanium compounds [(TiCp)(2)(mu-(eta(5)-C5Me4SiMeO)(2)- (mu-O)})(mu-Cl)][Q] (Q = ClB(C6F5)(3), 4B; ClAl(C6F5)(3), 4Al; Q = B(C6F5)(4), 4C) as the unique reaction products. Addition of [Ph3C][B(C6F5)(4)] to the mixture of isomers in 3 gave a mixture of complexes [(TiCpMe)(TiCp)(mu-(eta(5)-C5Me4SiMeO)(2)(mu-O)})][Q] (5aC and 5sC; Q = B(C6F5)(4)). With the remaining methyl ligand located at anti or syn positions depending on the methyl group being abstracted. DFT studies were carried out to determine the stability of the isomers of 2 and 3. to determine which chlorine atom in compound 2as was more easily eliminated,and also to clarify the transformation of isomer 2as into the mixture of isomers 3as. 3aa, and 3ss during the alkylation reaction.