1,4-Bis(trimethylsilyl)cyclopentadien | 38927-86-5

• 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: 1,4-Bis(trimethylsilyl)cyclopentadien
• 英文别名: Trimethyl-(4-trimethylsilylcyclopenta-1,3-dien-1-yl)silane
• CAS: 38927-86-5
• 化学式: C₁₁H₂₂Si₂
• 分子量: 210.467
• InChiKey: MPOLVSVWKHPEGP-UHFFFAOYSA-N

物化性质

• 沸点：
  165.8±40.0 °C(Predicted)
• 密度：
  0.84±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.0
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  1,4-Bis(trimethylsilyl)cyclopentadien 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以72%的产率得到
  参考文献：
  名称：

  Organolanthanide hydroxides; the synthesis and crystal structures of the samarocene and ytterbocene hydroxides [SmCp2″(μ-OH)2] and [YbCp2′(μ-OH)2][Cp″ = η5-C5 H3(SiMe3)2-1,3; Cp′ = η5-C5H4SiMe3]

  摘要：

  The organolanthanide(III) complexes [{SmCp2''(mu-OH)}2] (1) and [{YbCp2'(mu-OH)}2] (2) [Cp'' = eta-5-C5H3(SiMe3)2-1,3; Cp' = eta-5-C5H4SiMe3] were prepared from the appropriate lanthanocene(II) precursor [SmCp2''(THF)] (3) and [YbCp2'(OEt2)] (4), by treatment with water in an ethereal solution. The single crystal X-ray structures of 1 and 2 reveal that each complex is dimeric with bridging hydroxide groups, while NMR data indicate that these structures persist in aprotic media. The mean bond lengths Sm-O 2.40(2) and Sm-Cent(Cp'') 2.45 angstrom in crystalline 1 may be compared with Yb-O 2.29(2) and Yb-Cent(Cp') 2.33 angstrom in 2; while the angle O-Sm-O' in 1 is 76.6(6) and O-Yb-O' in 2 is 77.9(7)degrees (''Cent'' refers to the centroid of the C5 ring).

  DOI：

  10.1016/0022-328x(91)80040-q

文献信息

• Coordination of allenyl/propargyl group to samarium(III): the first crystal structures of η3-allenyl and η1-propargyl lanthanide complexes
  作者：Eiji Ihara、Motomi Tanaka、Hajime Yasuda*、Nobuko Kanehisa、Tatsuya Maruo、Yasushi Kai*

  DOI：10.1016/s0022-328x(00)00479-4

  日期：2000.10

  The synthesis and crystal structures of samarium complexes incorporating bridged Cp′SiMe2allenyl/propargyl ligands [Cp′=(Me3Si)2(C5H2)] are described. The reaction of a dilithium salt of [(Me3Si)2(C5H3)]SiMe2CH2CCSiMe3 (1a) with SmCl3 yielded an η3-allenyl complex [(Me3Si)2(C5H2)]SiMe2(η3-CCC[H]SiMe3)}SmCl3Li2(TMEDA)2 (2a) (TMEDA=N,N,N′,N′-tetramethylethylenediamine). On the other hand, the reaction

  的合成和晶体结构钐络合物的掺入桥接Cp'SiMe 2 allenyl/炔丙基配体的[Cp'=（ME 3 Si）的2（C 5 H ^ 2）]中描述。的二锂盐的反应〔（ME 3 Si）的2（C 5 H ^ 3）]森达2 CH 2 CCSiMe 3（1A）与SMCL 3产生的η 3 -allenyl复杂[（ME 3 Si）的2（C 5 H ^ 2）]森达2（η 3 -CCC[H ] SiMe 3）} SmCl 3 Li 2（TMEDA）2（2a）（TMEDA = N，N，N '，N'-四甲基乙二胺）。在另一方面，一个pH的二锂盐的反应3硅取代的配体[（ME 3 Si）的2（C 5 H ^ 3）]森达2 CH 2 CCSiPh 3（图1b）与SMCL 3产生的η 1 -炔丙基络合物[（Me 3 Si）2（C5 ħ 2）]森达2（η 1 -CHCCSiPh 3）} SM（TMEDA
• Synthesis and properties of sterically congested cyclopentadienes and their transition metal complexes
  作者：T.Jeffrey Clark、Christopher M. Killian、Sanjay Luthra、Terence A. Nile

  DOI：10.1016/0022-328x(93)83365-3

  日期：1993.12

  The synthesis of 1,3-dialkyl substituted cyclopentadienes, C5H4RR′, Cp′H (Va–g) (where R and R′ are tert-butyl, iso-propyl, neo-pentyl, cyclohexyl, or 1-methylcyclohexyl) is reported. These are synthesized by the nucleophilic addition of methyl or hydride anions to the corresponding 2-alkyl-6,6-dialkylfulvenes (IIIa–f) followed by hydrolysis. These substituted 1,3-cyclopentadienes have been converted

  1,3-二烷基取代的环戊二烯，C 5 H 4 RR'，Cp'H（Va–g）（其中R和R'为叔丁基，异丙基，新戊基，环己基或1-甲基环己基）。这些是通过将甲基或氢化物阴离子亲核加成到相应的2-烷基-6,6-二烷基富勒烯（IIIa–f）中，然后水解而合成的。这些取代的1,3-环戊二烯已转化为有机金属衍生物例如[CP'Fe（CO）2 ] 2，[CP'M（CO）3本人]（MMo或W）和CP' 22Fe。为了研究取代的环戊二烯基配体的空间和电子性质，已经研究了所选配合物的光谱和电化学性质。
• Supersize Cp! Tetrabenzo[<i>a</i>,<i>c</i>,<i>g</i>,<i>i</i>]fluorenyl complexes of yttrium
  作者：Jianlong Sun、David J. Berg、Brendan Twamley

  DOI：10.1139/cjc-2016-0485

  日期：2017.4

  5 kJ mol−1. The reaction of 1 with acidic hydrocarbons such as 1,3-bis(trimethylsilyl)cyclopentadiene or trimethylsilylacetylene results in protonolysis to form the mixed Cp derivative [(Tbf)C5H3(SiMe3)2}Y(CH2SiMe3)(THF)] (3) or [(Tbf)Y(CCSiMe3)2(THF)]n (4), respectively. In the case of 4, a small amount of the trinuclear cluster (Tbf)Y3(μ3-CCSiMe3)2(μ2-CCSiMe3)3(CCSiMe3)3(THF)2 (5) was isolated and

  四苯并[a,c,g,i]芴基(Tbf)钇二烷基配合物的合成，(Tbf)Y(CH2SiMe3)2(L)(L=四氢呋喃(THF)，1；L=bipy，2)，由报道了三（烷基）络合物 Y(CH2SiMe3)3(THF)2 的直接质子分解。1 和 2 的 X 射线晶体结构显示了 Tbf 配体通常观察到的螺旋扭曲。对 1 的动态核磁共振 (NMR) 研究表明，Tbf 螺旋反转（差向异构化或“摆动”）的障碍为 38.1 ± 0.5 kJ mol-1。1 与酸性烃（如 1,3-双（三甲基甲硅烷基）环戊二烯或三甲基甲硅烷基乙炔）的反应导致质子分解，形成混合 Cp 衍生物 [(Tbf)C5H3(SiMe3)2}Y(CH2SiMe3)(THF)] (3 ) 或 [(Tbf)Y(CCSiMe3)2(THF)]n (4)，分别。在 4 的情况下，少量的三核簇 (Tbf)Y3(μ3-CCSiMe3)2(μ2-CCS
• Substituted cyclopentadienyl ligands—10. Intramolecular steric interactions in [(η5-C5H3(SiMe3)2)Mo(CO)2(L)I]
  作者：Jeremy M. Smith、David P. White、Neil J. Coville

  DOI：10.1016/0277-5387(96)00188-x

  日期：1996.9

  Reaction of C5H4(SiMe(3))(2) with Mo(CO)(6) yielded [(mu(5)-C5H3(SiMe(3))(2))Mo(CO)(3)](2), which on addition of iodine gave [(eta(5)-C5H3(SiMe(3))(2))Mo(CO)(3)I]. Carbonyl displacement by a range of ligands : [L = P(OMe)(3), P(OPri)(3), P(O-o-tol)(3), PMe(3), PMe(2)Ph, PMePh(2), PPh(3), P(m-tol)(3)] gave the new complexes [(eta(5)-C5H3(SiMe(3))(2))Mo(CO)(2)(L)I]. For all L the trans isomer was the dominant, if not exclusive: isomer formed in the reaction. An NOE spectral analysis of [(eta(5)-C5H3(SiMe(3))(2))Mo(CO)(2)(L)I] [L = PMe(2)Ph, P(OMe)(3)] revealed that the L group resided on the sterically uncongested side of the cyclopentadienyl ligand and that the ligand did not access the congested side of the molecule. Quantification of this phenomenon [L = P(OMe)(3)] was achieved by means of the vertex angle of overlap methodology. This methodology revealed a steric preference with the trans isomer (less congestion of CO than I with an SiMe(3) group) being the more stable isomer for L = P(OMe)(3). Copyright (C) 1996 Elsevier Science Ltd
• Synthesis of the First Cluster Complexes Bearing Three Quadruply Bridging CO Ligands:  X-ray Crystal Structure of [C₅H₃(SiMe₃)₂]WRu₆(μ₃-H)- (CO)₁₈
  作者：Yun Chi、Chi-Jung Su、Shie-Ming Peng、Gene-Hsiang Lee

  DOI：10.1021/ja9720927

  日期：1997.11.1