LiC5H4SiMe2(allyl) | 195965-46-9

• 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: LiC5H4SiMe2(allyl)
• 英文别名: Lithium 1-[dimethyl(prop-2-en-1-yl)silyl]cyclopenta-2,4-dien-1-ide；lithium;cyclopenta-2,4-dien-1-yl-dimethyl-prop-2-enylsilane
• CAS: 195965-46-9
• 化学式: C₁₀H₁₅Si*Li
• 分子量: 170.256
• InChiKey: YGTOQGHCQWYOPM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.49
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  LiC5H4SiMe2(allyl) 以 四氢呋喃 为溶剂， 生成 {[4-(Allyl-dimethyl-silanyl)-cyclopenta-1,3-dienyl]-dimethyl-silanyl}-tert-butyl-amine
  参考文献：
  名称：

  (烯丙基甲硅烷基)(η-酰胺基甲硅烷基)-η5-环戊二烯基配体的锆和铪配合物：合成、结构和反应性

  摘要：

  二取代的环戊二烯 C5H4(SiMe2Cl)[SiMe2(CH2CH=CH2)] 通过锂盐 [Li{C5H4SiMe2(CH2CH=CH2)}] 与 SiMe2Cl2 的反应分离。然后用 NH2tBu 和 LiNH(2,6 -Me2C6H3) 得到（氨基甲硅烷基）环戊二烯 C5H4[SiMe2(CH2CH=CH2)][SiMe2(NHR)]，其进一步去质子化为二锂盐 [Li2{1-SiMe2NR-3-SiMe2(CH2CH=CH2)C5H3 }] (R = tBu, 2,6-Me2C6H3)。金属卤化物 ZrCl4(THF)2 和 HfCl4 与这些二锂盐反应，然后将所得二氯配合物烷基化，得到 (η 1 -酰胺基甲硅烷基)-η 5 - 环戊二烯基配合物 [M{η 5 C5H3(SiMe2-η 1 -NR)[SiMe2(CH2CH=CH2)]}X2](R =tBu, 2,6Me2C6H3; X

  DOI：

  10.1002/ejic.200500379

文献信息

• Allylsilylcyclopentadienyl Group 4 metal complexes: synthesis, structure and reactivity
  作者：Jesús Cano、Pilar Gómez-Sal、Georg Heinz、Gema Martı́nez、Pascual Royo

  DOI：10.1016/s0020-1693(02)01280-x

  日期：2003.3

  metallocene complexes using MeLi, MgMeCl, Mg(CH2Ph)Cl and Mg(CH2Ph)2(THF)2 afforded the monomethyl titanium [Ti(η5-C5H5)η5-C5H4SiMe2(CH2CHCH2)}ClMe] (15) and the dialkyl cyclopentadienyl [M(η5-C5H5)η5-C5H4SiMe2 (CH2CHCH2)}R2] (R=Me, M=Ti 16, Zr 18; R=CH2Ph, M=Ti 20, Zr 22), [Zrη5-C5H4SiMe2(CH2CHCH2)}2R2] (R=Me 17, CH2Ph 21) and indenyl derivatives [Zr(η5-C5H5)η5-C9H6SiMe2(CH2CHCH2)}R2] (R=Me 19, CH2Ph

  （Allyldimethyl）甲硅烷基取代的环戊二烯Ç 5 ħ 5森达2（CH 2 CHCH 2）（1）和茚Ç 9 ħ 7 1-森达2（CH 2 CHCH 2）（2）由反应合成森达的2（CH 2 CHCH 2）氯与NAC 5 ħ 5或LIC 9 ħ 7，分别。用n-BuLi和TlOEt金属化1得到相应的锂3和al 5盐。所述disilylcylopentadienesÇ 5 ħ 4 1-森达3 1-森达2（CH 2 CHCH 2）（6）和C 5 H ^ 4 1,1-[森达2（CH 2 CHCH 2）] 2通过使3与相应的氯硅烷反应来制备（7）。化合物7用TiCl 4进行反应4，得到单环戊二烯基化合物钛[Ti η 5 -C 5 H ^ 4森达2（CH 2 CHCH2）}氯3 ]（8），而5是用于制备二茂钛钛[Ti（η 5 -Cp）η 5 -C 5 H ^ 4森达2（CH
• Allyl Isomerization Mediated by Cyclopentadienyl Group 6 Metal Compounds
  作者：Eva Royo、Sergio Acebrón、Marta Elena González Mosquera、Pascual Royo

  DOI：10.1021/om700293a

  日期：2007.7.1

  amounts of ONMe3 permits isolation of pure compound 9 and [Wη5-C5H4Si(CH3)2(CH2CHCH2)}(CO)3]2 (10) in isolated yields of 80−90%. Coordination of the olefin pendant unit to the metal was detectable only by reaction of 5a and 7a with [CPh3][B(C6F5)4] to give the cationic species [Mη5-C5H4Si-(CH3)2(CH2CHCH2)}(CO)3][B(C6F5)4] (M = Mo (18), W (19)). Molecular structure determinations by X-ray diffraction

  在乙腈的加合物的温和的温度反应[M（CO）3（NCMe）3 ]（M =钼（1），W（2））与各种取代的环戊二烯的THF溶液，得到氢基衍生物[MH η 5 -C 5 R 4 Si（CH 3）2-（CH 2 CH CH 2）}（CO）3 ]（M = Mo，R = H（5a），R = CH 3（6），M = W，R = H（图7a）中，R = CH 3（图8a））和[卫生部η 5 -C 5 - [R 4R'}（CO）3 ]（R = CH 3，R'= H（16）； R = H，R'= SiMe 3（17）），分离产率为60-70％。衍生物的THF溶液5A，7A，和图8a经历环戊二烯基-拴系的烯丙基单元的异构化，得到相应的甲基乙烯基二甲基甲硅烷-η 5 -环戊二烯基氢基的化合物[MH η 5 -C 5 - [R 4的Si（CH 3）2（CH CHCH 3）}（CO）3 ]（M = Mo，R =
• Synthesis and characterization of η5-cyclopentadienyl–silylallyl niobium and tantalum complexes
  作者：Pilar Nicolás、Pascual Royo

  DOI：10.1016/j.ica.2004.09.017

  日期：2005.3

  Reaction of the disilylcyclopentadiene 1,1-[SiMe2(CH2CH=CH2)](2)C5H4 with NbCl5 gave the new allylsilyl-substituted monocyclopentadienyl niobium complex [Nbeta(5)-C5H4SiMe2(CH2CH=CH2)}Cl-4]. This compound was reacted with LiNHtBu or NH(2)tBu to give the imido derivative [Nbeta(5)-C5H4SiMe2(CH2CH=CH2) (NtBu)Cl-2], which was further alkylated to the imido alkyl complexes [Nbeta(5)-C5H4SiMe2(CH2CH=CH2)}(NtBu)Cl-2] (R=Me, CH2Ph) and [Nbeta(5)-C5H4SiMe2(CH2CH=CH2)}(NtBu)Cl (CH2Ph)]. Reaction of the imido complexes with the corresponding lithium cyclopentadienides gave the dicyclopentadienyl-imido complexes [M(eta(5)-C5R5)eta(5)-C5H4SiMe2(CH2CH=CH2)}(NtBu)Cl] (M = Nb, Ta; R = H, Me). Metallocene dichlorides [M(eta(5)-C5R5)eta(5)-C5H4SiMe2(CH2CH=CH2)}Cl-2] (M = Nb, Ta; R = H, Me) were easily prepared by reduction with Na/Hg and simultaneous transmetallation of [Ta(eta(5)-C5R5)Cl-4] with Li[C5H4SiMe2(CH2CH=CH2)] and of [Nbeta(5)-C5H4SiMe2(CH2CH=CH2)}Cl-4] with Li(C5R5). All of the new compounds have been characterized by elemental analysis, and IR and NMR spectroscopy. (c) 2004 Elsevier B.V. All rights reserved.
• Allyldimethylsilylcyclopentadienyl Hafnium Complexes:  Formation and Trapping of Hafnocenium Cations
  作者：Gema Martínez、Pascual Royo

  DOI：10.1021/om050437l

  日期：2005.9.1

  The mixed silyl-stannyl-cyclopentadiene C5H4[SiMe2(CH2CH=CH2)] [Sn(nBu)(3)] was synthesized by reaction of the lithium salt Li[C5H4SiMe2(CH2CH=CH2)}] with the corresponding chlorotrialkyltin and then reacted with HfCl4 to prepare the monocyclopentadienyl complex [Hfeta(5)-C5H4SiMe2(CH2CH=CH2)}Cl-3 center dot DME] (DME = dimethoxyethane). Reaction of this compound with Na(C5H5) or Li(C5H5) afforded low yields of the dichloro hafhocene [Hf(eta(5)-C5H5)eta(5)-C5H4SiMe2(CH2CH=CH2)}Cl-2], which was also isolated more efficiently by transmetalation of the lithium salt Li[C5H4SiMe2(CH2CH=CH2)}] with [Hf(eta(5)-C5H5)Cl-3 center dot DME]. Alkylation of the mono- and dicyclopentadienyl complexes with MgCl(CH2Ph) or LiMe gave the tribenzyl monocyclopentadienyl [Hf(eta(5)-C5H4SiMe2(CH2CH=CH2)}(CH2Ph)(3)] or the dialkyl hafhocene derivatives [Hf(eta(5)-C5H5)eta(5)-C5H4SiMe2(CH2CH=CH2)R-2] (R = Me, CH2Ph). The reaction of the dibenzyl hafhocene with the Lewis acid B(C6F5)(3) was monitored by NMR spectroscopy at variable temperature. Formation of the hafhocenium cationic species [Hf(eta(5) -C5H5)eta(5)-C5H4SiMe2(CH2-eta(2)-CH=CH2)}(CH2Ph)(+) was initially observed, which then slowly transformed into the metallacyclic alkyl [Hf(eta(5)-C5H5)eta(5)-C5H4SiMe2CH2CH(CH2Ph)eta(1)-CH2}](+) cation, resulting from the benzyl migratory insertion of the allylic alkene moiety. Reaction of these intermediate cationic species with KOtBu gave the neutral dicyclopentadienyl hafhocene compounds [Hf(eta(5)-C5H5)eta(5)-C5H4SiMe2(CH2CH=CH2)}(CH2Ph)(OtBu)] and [Hf(eta(5)-C5H5)eta(5)-C5H4SiMe2[CH2CH(CH2Ph)-eta(1)-CH2]}(OtBu)], which were characterized by elemental analyses and NMR spectroscopy.