1-(chlorodimethylsilyl)-1-(trimethylsilyl)cyclopentadiene | 96502-49-7

• 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: 1-(chlorodimethylsilyl)-1-(trimethylsilyl)cyclopentadiene
• 英文别名: Chloro-dimethyl-(1-trimethylsilylcyclopenta-2,4-dien-1-yl)silane
• CAS: 96502-49-7
• 化学式: C₁₀H₁₉ClSi₂
• 分子量: 230.885
• InChiKey: IOLZVGNKAXWBGK-UHFFFAOYSA-N

物化性质

• 沸点：
  69-74 °C(Press: 2-3 Torr)
• 密度：
  0.94±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.17
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• 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：

  1-(chlorodimethylsilyl)-1-(trimethylsilyl)cyclopentadiene 、 五氯化铌 以 甲苯 为溶剂， 以90%的产率得到[Nb(η(5)-C5H4(SiClMe2))Cl4]
  参考文献：
  名称：

  Chlorosilyl-Substituted Monocyclopentadienyl Niobium Chloro, Imido Chloro, and Benzyl Complexes. X-ray Molecular Structure of [{(NbCl₂)₂(μ-O)(μ-Cl)₂}{(η⁵-C₅H₄)₂(Me₂SiOSiMe₂)}]

  摘要：

  We report the synthesis of 1-(chloromethylphenylsilyl)cyclopentadie. The reaction of a toluene/CH2Cl2 suspension of NbCl5 with 1-(SiClMeX)-1-(SiMe3)C5H4 (X = Me, Ph) leads to the monocyclopentadienyl derivatives [M{eta(5)-C5H4(SiClMeX)}Cl-4] (X = Me, Ph) in 90 and 78% yields, respectively. Reaction of 1 equiv of water with [M(eta(5)-C5H4(SiClMe2))Cl-4] in toluene takes place with elimination of HCl, resulting in formation of the dinuclear niobium oxo derivative [((NbCl2)(2)(mu-O)(mu-Cl)(2))((eta(5)-C5H4)(2)(Me2SiOSiMe2)}]. Reaction of the complexes [M{eta(5)-C5H4(SiClMeX))Cl-4] with (LiNHBu)-Bu-t and NEt3 in toluene leads to the half-sandwich imido complexes [Nb{eta(5)-C5H4(siClMeX))Cl-2((NBu)-Bu-t)] (X = Me, Ph), which react at room temperature with 1 equiv of Mg(CH2Ph)(2)(THF)(2) to give the imido dibenzyl complexes [Nb{eta(5)-C5H4(siClMeX))(CH2Ph)(2)((NBu)-Bu-t)] (X = Me, Ph). The reaction of the chloro imido complexes [Nb{eta(5)-C5H4(SiClMeX))Cl-2((NBu)-Bu-t)] with excess Mg(CH2Ph)(2)(THF)(2) on heating for 2-3 days to 80-90 and 50-60 degrees C, respectively, takes place, affording the totally alkylated complexes [Nb{eta(5)-C5H4[si(CH2Ph)MeX])(CH2Ph)(2)((NBu)-Bu-t) (X = Me, Ph). The chloro benzyl derivative [Nb{eta(5)-C5H4(SiClMe2))(CH2Ph)Cl((NBu)-Bu-t)], which could not be prepared by addition of the stoichiometric amount of the alkylating agent, was isolated in quantitative yield by heating a mixture of the dichloro and dibenzyl complexes in toluene at 120 degrees C for 4 h. The 18-electron imido eta(2)-iminoacyl derivatives [Nb{(eta(5)-C5H4(SiMeXY))R((NBu)-Bu-t){eta(2)-C(CH2Ph=N- (2,6-Me2C6H3))] (R = CH2Ph, X = Cl, Y = Me, Ph; R = CH2Ph, X = CH2Ph, Y = Me, Ph; R Cl, X = Cl, Y = Me) are formed when the isocyanide CN(2,6-Me2C6H3) is added to a hexane solution of the benzylimido complexes. The molecular structure of the oxo complex [{(NbCl2)(2)(mu-O)(mu-Cl)(2)){(eta(5)-C5H4)(2)(Me2SiOSiMe2)}] has been determined by X-ray diffraction methods.

  DOI：

  10.1021/om970876n
• 作为产物：
  描述：

  三甲硅烷基环戊二烯 、 二氯二甲基硅烷 生成 1-(chlorodimethylsilyl)-1-(trimethylsilyl)cyclopentadiene
  参考文献：
  名称：

  JONES, P. R.;ROZELL, J. M. ,, JR.;CAMPBELL, B. M., ORGANOMETALLICS, 1985, 4, N 8, 1321-1324

  摘要：

  DOI：

文献信息

• Synthetic and reactivity studies of mono- and dicyclopentadienyl titanium, zirconium and hafnium complexes with the chlorodimethylsilyl-cyclopentadienyl ligand. X-ray molecular structure of Hf{(η5-C5H4)SiMe2OSiMe2(η5-C5H4)}Cl2 and Zr(η5-1,3-tBu2C5H3)(η5-C5H4SiMe2-η-NtBu)Cl
  作者：Santiago Ciruelos、Alfredo Sebastián、Tomás Cuenca、Pilar Gómez-Sal、Antonio Manzanero、Pascual Royo

  DOI：10.1016/s0022-328x(00)00213-8

  日期：2000.6

  Reaction of the disilylated cyclopentadiene C5H4(SiClMe2)(SiMe3) with HfCl4, in heptane, gave the monocyclopentadienyl complex Hf(η5-C5H4SiClMe2)Cl3 (1c). Addition of two equivalents of C5H5(SiClMe2) to a solution of MCl4, in toluene under reflux and in the presence of two equivalents of NEt3, afforded the dichloro derivatives M(η5-C5H4SiClMe2)2Cl2 [M=Ti (2a), Hf (2c)]. Compounds 2a and 2c react with a

  的二甲硅烷基化的环戊二烯的C反应5 ħ 4（SiClMe 2）（森达3）用的HfCl 4，在庚烷中，得到单环戊二烯基络合物的Hf（η 5 -C 5 H ^ 4 SiClMe 2）氯3（1C）。的C两个当量的另外5 ħ 5（SiClMe 2）到的MC1中的溶液4在回流下和在网的两个当量的存在下，在甲苯3，得到二氯衍生物M（η 5 -C 5 H ^ 4 SiClMe2）2 Cl 2 [M ＝ Ti（2a），Hf（2c）]。化合物2A和2C与水与SiCl键的选择性水解的化学计量量的反应，得到四甲基二硅氧烷桥连络合物diciclopentadienylμ（η 5 -C 5 H ^ 4）森达2 OSiMe 2（η 5 -C 5 H ^ 4）} Cl 2 [M ＝ Ti（3a），Hf（3c）]。三氯金属的化合物反应M（η 5 -C 5 H ^ 4SiClMe 2）氯3与铊（1,3-吨卜2 ç 5 ħ
• Ciruelos, Santiago; Cuenca, Tomás; Gómez-Sal, Pilar, Organometallics, 1995, vol. 14, # 1, p. 177 - 185
  作者：Ciruelos, Santiago、Cuenca, Tomás、Gómez-Sal, Pilar、Manzanero, Antonio、Royo, Pascual

  DOI：——

  日期：——
• Synthesis of sandwich and half-sandwich complexes of Ti, Zr and Hf containing η5-C5H4SiMe2Cl ligand. Molecular structure of [TiCl2(μ-OSiMe2-η5-C5H4)]2
  作者：Andrew V. Churakov、Dmitry A. Lemenovskii、Ludmila G. Kuz'mina

  DOI：10.1016/0022-328x(94)05241-3

  日期：1995.3

  Reactions of (C(5)H(4)SiMe(3))SiMe(2)Cl (1) and (mu-SiMe(2)C(5)H(4))(2) (2) with Ti, Zr and Hf tetrachlorides lead to the complexes M(eta(5)-C(5)H(4)SiMe(2)Cl)Cl-3 (M = Ti, 3a; Zr, 3b; Hf, 3c). Treatment of 3a with cyclopentadienyl thallium affords Ti(eta(5)-C5H5)(eta(5)- C(5)H(4)SiMe(2)Cl)Cl-2 (4). Dimeric oxo-derivative [TiCl2(mu-OSiMe(2)-eta(5)-C5H4)](2) (5) was prepared by slow hydrolysis of 3a. Structure of 5 was determined by X-ray diffraction.
• Silenes and silenoids. 9. The synthesis of polyfunctional bis(Group 14)-substituted cyclopentadienes via a novel cleavage reaction of silicon-carbon bonds by chloride ion
  作者：James M. Rozell、Paul Ronald Jones

  DOI：10.1021/om00131a025

  日期：1985.12
• Synthesis, characterization and styrene polymerization behavior of alkoxysilyl-substituted monocyclopentadienyltitanium(IV) complexes
  作者：Milan Erben、Jan Merna、Ondřej Hylský、Jana Kredatusová、Antonín Lyčka、Libor Dostál、Zdeňka Padělková、Martin Novotný

  DOI：10.1016/j.jorganchem.2012.11.040

  日期：2013.2

  Trimethylsilylcyclopentadienes bearing alkoxysilyl functionality, C5H4(SiMe3)(SiMe2OR), where R is Me (2), i-Pr (3) and t-Bu (4), were prepared and characterized. Methoxy derivative 2 reacts with TiCl4 giving unstable [Ti(eta(5)-C5H4SiMe2OMe)Cl-3] (5), which is slowly transformed to chlorosilyl complex [Ti(eta(5)-C5H4SiMe2Cl)Cl-3] (6) and a mixture of cyclopentadienyltitanium(IV) methoxides on heating. Fully alkoxylated derivatives of the type [Ti(eta(5)-C5H4SiMe2OR)(OR)(3)] [R = Me (7), i-Pr (8), t-Bu (9)] and Ti[eta(5)-C5H4SiMe(OMe)(2)](OMe)(3)} (10), were synthesized in low-to-moderate yields from respective chlorosilylcyclopentadienyltitanium trichlorides. All prepared alkoxysilyl compounds were characterized by spectroscopic techniques including Si-29 NMR. Polymerization activity of 7-10 in the presence of methylaluminoxane was determined and compared with [TiCp(OMe)(3)] and corresponding trimethylsilyl-substituted compounds [Ti(eta(5)-C5H4SiMe3)(OR)(3)], where R is Me, i-Pr and t-Bu. The highest conversion of styrene has been observed in systems based on [Ti(eta(5)-C5H4SiMe3)(OMe)(3)], [TiCp(OMe)(3)] and [Ti(eta(5)-C5H4SiMe3)(OBut)(3)], respectively. The new alkoxysilyl compounds 7-10 have significantly lower activity of 500-1800 kg of polystyrene/(mol Ti mol styrene h). All prepared polystyrenes showed both high melting point and high degree of syndiotacticity as determined by DSC and NMR measurements. (C) 2012 Elsevier B.V. All rights reserved.