dimethylbis(3-tert-butylcyclopentadienyl)silane | 126116-82-3

• 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: dimethylbis(3-tert-butylcyclopentadienyl)silane
• 英文别名: dimethylbis(t-butylcyclopentadienyl)silane；Me2Si(3-tBuC5H3)2；Silane, bis[3-(1,1-dimethylethyl)-2,4-cyclopentadien-1-yl]dimethyl-；bis(3-tert-butylcyclopenta-2,4-dien-1-yl)-dimethylsilane
• CAS: 126116-82-3
• 化学式: C₂₀H₃₂Si
• 分子量: 300.56
• InChiKey: ANJHTOUUADABQR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.52
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  dimethylbis(3-tert-butylcyclopentadienyl)silane 在 正丁基锂 作用下， 以 乙醚 为溶剂， 生成 Li2[Me2Si(Cp(t-Bu))2]
  参考文献：
  名称：

  通过环戊二烯基和氯化物配体的可逆交换控制 ansa-Zirconocene 立体化学

  摘要：

  Li2[Me2Si(3-R-C5H3)2]盐与Zr{Me3SiN(CH2)3NSiMe3}Cl2(THF)2在THF中反应定量得到外消旋Me2Si(3-R-C5H3)2Zr{Me3SiN(CH2)具有 100% 立体选择性的 3NSiMe3} 锆茂。核磁共振监测研究表明，这些反应最初形成外消旋/内消旋混合物，经过异构化成为纯外消旋。异构化需要 Cp-enantioface 交换，并由氯离子催化，从 Me2Si(3-R-C5H3)2Zr{Me3SiN(CH2)3NSiMe3} 可逆地置换 Cp-。所选配合物的动力学分析显示异构化速率对茂金属和氯化物浓度的一级依赖性。可逆 Cp-/Cl- 交换对于 {ansa-bis-Cp}ZrCl2 和非桥连 Cp2ZrCl2 复合物也很容易。

  DOI：

  10.1021/ja0681523
• 作为产物：
  描述：

  二氯二甲基硅烷 、 tert-butylcyclopentadienyl lithium 以 四氢呋喃 、 正戊烷 为溶剂， 反应 3.0h， 以90%的产率得到dimethylbis(3-tert-butylcyclopentadienyl)silane
  参考文献：
  名称：

  柄型茂金属衍生物：XVII。IV组茂金属衍生物的外消旋和内消旋非对映异构体，具有对称取代的二甲基硅烷二基桥接配体骨架。R，S -Me 2 Si（3-t-Bu-5-MeC 5 H 2）2 ZrCl 2的晶体结构

  摘要：

  的外消旋的形成和内消旋的非对映体取代柄-zirconocenes（CH 3）2的Si（1-C 5 H ^ 3 -3-R）2的ZrCl 2（R叔丁基，三甲基甲硅烷，α，α-二甲基苄基和1-已经在各种条件下研究了由二甲基硅烷二基桥连的对称取代的双环戊二烯基二价阴离子衍生物和ZrCl 4 ·2THF衍生的-苯基环己基）。在所有情况下，Rac /内消旋比均接近1。对于类似的钛和ha与R 3三甲基甲硅烷基的配合物，观察到相似的产物比率。rac / meso显着增加当在（CH 3）2 Si（1-C 5 H 2 -3-R-5-CH 3）2 ZrCl 2（RCH（CH 3）2，C（CH 3）3）。有人建议，用一个η中间体1结合的环配位体控制的立体化学过程袢茂金属形成。的晶体结构R，S - （CH 3）2的Si（1-C 5 H ^ 2 -3-C（CH 3）3 -5-CH 3）2 ZrCl 2被报道。

  DOI：

  10.1016/0022-328x(89)85186-1

文献信息

• 8-Sila-4-stanna-s-tetrahydroindacenes as synthons for Me2Si-bridged zirconocenes: formation from biscyclopentadienyl silanes by reaction with aminostannanes
  作者：Mario Hüttenhofer、Frank Schaper、Hans-Herbert Brintzinger

  DOI：10.1016/s0022-328x(02)01775-8

  日期：2002.10

  Alkyl-substituted bis(cyclopentadienyl)dimethylsilanes react with Me2Sn(NEt2)2 and with (Me2N)4Sn to yield correspondingly substituted, meso-configurated RS-8-sila-4-stanna-s-tetrahydroindacene and axially symmetric RR,SS-4-spiro-bis(8-sila-4-stanna-s-tetrahydroindacene) compounds, respectively, which are stereoselectively converted by reaction with ZrCl4 to the corresponding meso- and rac-configurated

  烷基取代的双（环戊二烯基）dimethylsilanes与我反应2的Sn（NET 2）2，并用（ME 2 N）4的Sn，得到相应substituiertem，内消旋-构型RS -8-硅杂-4- stanna-小号-tetrahydroindacene和轴向对称RR，SS -4-螺双（8-羟基硅杂-4- stanna-小号-tetrahydroindacene）化合物分别哪些是立体选择性地通过与转化的ZrCl 4为相应的内消旋-和外消旋-构型袢-zirconocene络合物。
• Synthesis of Me₂Si-Bridged <i>ansa</i>-Zirconocenes by Amine Elimination
  作者：Gary M. Diamond、Richard F. Jordan、Jeffrey L. Petersen

  DOI：10.1021/om9601054

  日期：1996.9.17

  Me(2)Si-bridged ansa-zirconocenes of interest for a-olefin polymerization catalysis are prepared in good yield by amine elimination reactions. The reaction of Me(2)Si(1-C5H4-3-(t)Bu)(2) (3) and Zr(NMe(2))(4) affords Me(2)Si(1-C5H3-3-(t)Bu)(2)Zr(NMe(2))(2) (4) in 95% NMR yield (rac/meso = 1/2) and pure meso-4 in 38% isolated yield. The reaction of Me(2)Si(1-C5H3-2-Me-4-(t)Bu)(2) (6) with Zr(NMe(2))(4) affords Me(2)Si(1-C5H2-2-Me-4-(t)Bu)(2)Zr(NMe(2))(2) (7) in 90% NMR yield (rac/meso = 2.5/1) and pure rac-7 in 52% isolated yield. The 1/2 rac-4/meso-4 and 2.5/1 rac-7/meso-7 ratios are the thermodynamic ratios, and the rac/meso isomerizations are catalyzed by NMe(2)H via reversible Zr-Cp bond aminolysis. The thermodynamic bias for meso-4 is ascribed to the ease of distortion of the metallocene framework of this diastereomer by a lateral deformation which reduces steric crowding between the amide ligands and the Cp substituents. The reaction of 6 and Zr(NEt(2))(4) proceeds only in 1,2-dichlorobenzene at 180 degrees C, affording Me(2)Si(1-C5H2-2-Me-4-(t)Bu)(2)ZrCl2 (rac-1) in 35% NMR yield (rac/meso = 3/1). The reaction of 6 and the piperidide complex Zr(NC5H10)(4) (m-xylene, 140 degrees C, 24 h) affords rac-Me(2)Si(1-C5H2-2-Me-4-(t)Bu)(2)Zr(NC5H10)(2) (rac-9) in 35% NMR yield (no meso detected) and pure rac-9 in 7% isolated yield. The reaction of 6 and the pyrrolidide complex Zr(NC4H8)(4) (m-xylene, 90 degrees C, 4h) affords Me(2)Si(1-C5H2-2-Me-4-(t)Bu)(2)Zr(NC4H8)(2) (10) in 80% NMR yield (rac/meso = 3/1) and pure rac-10 in 39% isolated yield. The molecular structure of rac-10 was determined by X-ray crystallography and exhibits severe crowding between the amide ligands and the Cp substituents. Treatment of rac-7 or rac-10 with Me(3)SiCl results in clean conversion to rac-1 without isomerization.
• Synthesis and characterization of a series of sila-bridged diiron complexes (E)[(η5-t-BuC5H3)Fe(CO)]2(μ-CO)2 (E=Me2Si, Me2SiSiMe2, Me2SiOSiMe2). The molecular structures of cis- and trans-(Me2Si)[η5-t-BuC5H3)Fe(CO)]2(μ-CO)2
  作者：Yongqiang Zhang、Shansheng Xu、Gonglu Tian、Xiuzhong Zhou、Sun Jie

  DOI：10.1016/s0022-328x(97)00462-2

  日期：1998.2

  Binuclear iron complexes (E)[(eta(5)-t-BuC5H3)Fe(CO)](2)(mu-CO)(2) [E = Me2Si (1), Me2SiOSiMe2(3)] were prepared by reaction of Fe(CO)(5) with the corresponding cyclopentadienyl ligands in boiling xylene. Like the analogue (Me2SiSiMe2)[(eta(5)-t-BuC5H3)Fe(CO)](2)(mu-CO)(2) (2) reported previously, they are also found to exist as a mixture of cis and trans isomers that have been separated by preparative TLC. To examine the effect of larger substituents on the formation of isomers, the analogue (Me2Si)[eta(5)C(5)H(3)(t-heptyl)}Fe(CO)](2)(mu-CO)(2) (4) was also synthesized by the same approach. The molecular structures of cis- and trans-(Me2Si)[(eta(5)-t-BuC5H3)Fe(CO)](2)(mu-CO)(2) have been determined by X-ray diffraction. (C) 1998 Elsevier Science S.A.
• Synthesis of an ansa-Zirconocene via a NovelS4-Symmetric Spirobis(silastannaindacene) Compound
  作者：Mario Hüttenhofer、Frank Schaper、Hans H. Brintzinger

  DOI：10.1002/(sici)1521-3773(19980904)37:16<2268::aid-anie2268>3.0.co;2-y

  日期：1998.9.4

  A stereoselective reaction of Sn(NMe2 )4 with the silyl-bridged bis(cyclopentadienyl) derivative 1 generates the novel spiro compound 2, in which two C2 -symmetric six-membered rings of opposite configuration are joined at a tin center: One ring is R,R-, and the other S,S-configured. Subsequent reaction with two equivalents of ZrCl4 affords, by stereoselective Sn/Zr exchange, exclusively the C2 -symmetric isomer of the ansa-zirconocene rac-3.
• Control of <i>ansa</i>-Zirconocene Stereochemistry by Reversible Exchange of Cyclopentadienyl and Chloride Ligands
  作者：Richard M. Buck、Nawaporn Vinayavekhin、Richard F. Jordan

  DOI：10.1021/ja0681523

  日期：2007.3.1

  to pure rac. The isomerization requires Cp−enantioface exchange and is catalyzed by chloride ion, which reversibly displaces Cp- from Me2Si(3-R-C5H3)2ZrMe3SiN(CH2)3NSiMe3}. Kinetic analyses for selected complexes showed first-order dependence of the isomerization rate on both metallocene and chloride concentrations. Reversible Cp-/Cl- exchange is also facile for ansa-bis-Cp}ZrCl2 and nonbridged Cp2ZrCl2

  Li2[Me2Si(3-R-C5H3)2]盐与ZrMe3SiN(CH2)3NSiMe3}Cl2(THF)2在THF中反应定量得到外消旋Me2Si(3-R-C5H3)2ZrMe3SiN(CH2)具有 100% 立体选择性的 3NSiMe3} 锆茂。核磁共振监测研究表明，这些反应最初形成外消旋/内消旋混合物，经过异构化成为纯外消旋。异构化需要 Cp-enantioface 交换，并由氯离子催化，从 Me2Si(3-R-C5H3)2ZrMe3SiN(CH2)3NSiMe3} 可逆地置换 Cp-。所选配合物的动力学分析显示异构化速率对茂金属和氯化物浓度的一级依赖性。可逆 Cp-/Cl- 交换对于 ansa-bis-Cp}ZrCl2 和非桥连 Cp2ZrCl2 复合物也很容易。