双(环戊二烯基)甲烷 | 79249-50-6

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 中文名称: 双(环戊二烯基)甲烷
• 英文名称: dicyclopentadienylmethane
• 英文别名: bis(cyclopentadienyl)methane；5-(cyclopenta-2,4-dien-1-ylmethyl)cyclopenta-1,3-diene
• CAS: 79249-50-6
• 化学式: C₁₁H₁₂
• 分子量: 144.216
• InChiKey: ZLXSLQWIWAKSSS-UHFFFAOYSA-N

物化性质

• 沸点：
  220.1±7.0 °C(Predicted)
• 密度：
  0.999±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  thallium (I) ethoxide 、 双(环戊二烯基)甲烷 以 乙醇 为溶剂， 以60%的产率得到bis(cyclopentadienylthallium)methane
  参考文献：
  名称：

  Bis(cyclopentadienylthallium)methane: A versatile intermediate for the synthesis of dinuclear cyclopentadienylmetal carbonyl complexes

  摘要：

  DOI：

  10.1016/0022-328x(86)80298-4
• 作为产物：
  描述：

  二氯甲烷 、 环戊二烯 在 sodium 作用下， 以 四氢呋喃 为溶剂， 反应 2.9h， 以61%的产率得到双(环戊二烯基)甲烷
  参考文献：
  名称：

  Carbon-carbon bond formation in dinuclear dialkyl complexes. Reactions of [CpCo(CO)R]2 (R = methyl, ethyl, or 2,2,2-trifluoroethyl) and (C11H10)Co2(CO)2(CH3)2 with carbon monoxide and triphenylphosphine

  摘要：

  DOI：

  10.1021/ja00336a026

文献信息

• Photochemical reactions of [CH₂(η⁵-C₅H₄)₂][Rh(C₂H₄)₂]₂with silanes: evidence for Si–C and C–H activation pathways
  作者：Jenny L. Cunningham、Simon B. Duckett

  DOI：10.1039/b417171c

  日期：——

  Photochemical reaction of [CH2(η5-C5H4)2][Rh(C2H4)2]21 with dmso led to the stepwise formation of [CH2(η5-C5H4)2][Rh(C2H4)2][Rh(C2H4)(dmso)] 2a and [CH2(η5-C5H4)2][Rh(C2H4)(dmso)]22b. Photolysis of 1 with vinyltrimethylsilane ultimately yields three isomeric products of [CH2(η5-C5H4)2][Rh(CH2CHSiMe3)2]2, 3a,3b and 3c which are differentiated by the relative orientations of the vinylsilane. When this reaction is undertaken in d6-benzene, H/D exchange between the solvent and the α-proton of the vinylsilane is revealed. In addition evidence for two isomers of the solvent complex [CH2(η5-C5H4)2][Rh(C2H4)2][Rh(C2H4)(η2-toluene)] was obtained in these and related experiments when the photolysis was completed at low temperature without substrate, although no evidence for H/D exchange was observed. Photolysis of 1 with Et3SiH yielded the sequential substitution products [CH2(η5-C5H4)2][Rh(C2H4)2][Rh(C2H4)(SiEt3)H] 4a, [CH2(η5-C5H4)2][Rh(C2H4)(SiEt3)H]24b, [CH2(η5-C5H4)2][Rh(C2H4)(SiEt3)H][Rh(SiEt3)2(H)2] 4c and [CH2(η5-C5H4)2][Rh(SiEt3)2(H)2]24d; deuteration of the α-ring proton sites, and all the silyl protons, of 4d was demonstrated in d6-benzene. This reaction is further complicated by the formation of two Si–C bond activation products, [CH2(η5-C5H4)2][RhH(μ-SiEt2)]25 and [CH2(η5-C5H4)2][(RhEt)(RhH)(μ-SiEt2)2] 6. Complex 5 was also produced when 1 was photolysed with Et2SiH2. When the photochemical reactions with Et3SiH were repeated at low temperatures, two isomers of the unstable C–H activation products, the vinyl hydrides [CH2(η5-C5H4)2][Rh(SiEt3)H}Rh(SiEt3)}(μ-η1,η2-CHCH2)] 7a and 7b, were obtained. Thermally, 4c was shown to form the ring substituted silyl migration products [(η5-C5H4)CH2(C5H3SiEt3)][Rh(SiEt3)2(H)2]28 while 4b formed [CH2(C5H3SiEt3)2][Rh(SiEt3)2(H)2]2 (9a and 9b) upon reaction with excess silane. The corresponding photochemical reaction with Me3SiH yielded the expected products [CH2(η5-C5H4)2][Rh(C2H4)2][Rh(C2H4)(SiMe3)H] 10a, [CH2(η5-C5H4)2][Rh(C2H4)(SiMe3)H]210b, [CH2(η5-C5H4)2][Rh(C2H4)(SiMe3)H][Rh(SiMe3)2(H)2] 10c and [CH2(η5-C5H4)2][Rh(SiMe3)2(H)2]210d. However, three Si–C bond activation products, [CH2(η5-C5H4)2][(RhMe)(RhH)(μ-SiMe2)2] 11, [CH2(η5-C5H4)2][(RhSiMe3})(RhMe)(μ-SiMe2)2] 12 and [CH2(η5-C5H4)2][(RhSiMe3})(RhH)(μ-SiMe2)2] 13 were also obtained in these reactions.

  [ (η5-C5H4)2][Rh(C2H4)2]21与dmso的光化学反应导致[ (η5- )2][Rh( )2][Rh( )(dmso)]2a和[ (η5- )2][Rh( )(dmso)]22b的逐步形成。1与乙烯基三甲基硅烷的光解反应最终产生[ (η5- )2][Rh( CHSiMe3)2]2的三种异构体产物3a、3b和3c，它们通过乙烯基硅烷的相对取向区分。当此反应在d6-苯中进行时,揭示了溶剂与乙烯基硅烷的α-氢之间的H/D交换。此外,在这些及相关实验中,当光解在低温下完成且无底物时,获得了溶剂络合物[ (η5- )2][Rh( )2][Rh( )(η2-甲苯)]两种异构体的证据,尽管未观察到H/D交换的证据。1与Et3SiH的光解反应产生顺序取代产物[ (η5- )2][Rh( )2][Rh( )(SiEt3)H]4a、[ (η5- )2][Rh( )(SiEt3)H]24b、[ (η5- )2][Rh( )(SiEt3)H][Rh(SiEt3)2(H)2]4c和[ (η5- )2][Rh(SiEt3)2(H)2]24d;在d6-苯中证明了4d的α-环质子位点和所有硅基质子的氘化作用。该反应进一步复杂化,形成两种Si-C键活化产物,[ (η5- )2][RhH(μ-SiEt2)]25和[ (η5- )2][(RhEt)(RhH)(μ-SiEt2)2]6。当1与Et2SiH2光解时也生成了5。当在低温下重复Et3SiH的光化学反应时,获得了不稳定的C-H活化产物、乙烯基氢化物[ (η5- )2][Rh(SiEt3)H}Rh(SiEt3)}(μ-η1,η2-CH )]7a和7b的两种异构体。热力学上,4c被证明形成环取代的硅基迁移产物[(η5- )CH2(C5H3SiEt3)][Rh(SiEt3)2(H)2]28,而4b与过量硅烷反应形成[ (C5H3SiEt3)2][Rh(SiEt3)2(H)2]2(9a和9b)。对应的光化学反应与Me3SiH产生预期的产物[ (η5- )2][Rh( )2][Rh( )(SiMe3)H]10a、[ (η5- )2][Rh( )(SiMe3)H]210b、[ (η5- )2][Rh( )(SiMe3)H][Rh(SiMe3)2(H)2]10c和[ (η5- )2][Rh(SiMe3)2(H)2]210d。然而,这些反应中还获得了三种Si-C键活化产物,[ (η5- )2][(RhMe)(RhH)(μ-SiMe2)2]11、[ (η5- )2][(RhSiMe3})(RhMe)(μ-SiMe2)2]12和[ (η5- )2][(RhSiMe3})(RhH)(μ-SiMe2)2]13。
• Ligand exchange photochemistry of M2(CO)4( μ−η5,η5-C5H4CH2C5H4) (M  Fe or Ru) and thermal acetylene exchange of Ru2(CO)( μ-CO)[μ−η1:η1-(C6H5)2C2]( μ−η5, η5-C5H4CH2C5H4) The molecular structures of Ru2(CO)( σ-C6H5)( μ-CO)[ μ-P(C6H5)2]( μ−η5,η5-C5H4CH2C5H4) and Ru2(CO)( μ-CO)[ μ-η1,η3-C6H5CC(C6H5)O]- (μ-η5,η5-C5H4CH2C5H4)
  作者：Thomas E. Bitterwolf、Jay L. Haener、Joyce E. Shade、Arnold L. Rheingold、Glenn P.A. Yap

  DOI：10.1016/s0022-328x(96)06770-8

  日期：1997.11

  R = CH3O2C and C6H5. Reaction of Ru2(CO)4(μ−η5,η5-C5H4CH2C5H4) with triphenylphosphine under photochemical conditions resulted in loss of two carbon monoxide ligands nad PC insertion by ruthenium to yield Ru2(CO)(σ-C6H5)μ-CO)[μ-P(C6H5)2](μ−η5,η5-C5H4CH2C5H4). Photolysis of Ru2(CO)4(μ−η5,η5-C5H4CH2C5H4) with diphenylacetylene gave the previously reported Ru2(CO)2(μ-CO)[μ−η1:η1-(C6H5)2C2](μ−η5,η5-C5H4CH2C5

  的Fe的光解2（CO）4（μ - η 5，η 5 -C 5 H ^ 4 CH 2 C ^ 5 ħ 4）中的膦或亚磷酸酯导致形成简单的羰基取代产物的Fe存在2（CO）（μ -CO）2 L（μ - η 5，η 5 -C 5 H ^ 4 CH 2 C ^ 5 ħ 4）或Fe 2（μ-CO）2大号2（μ - η 5，η 5 -C 5 H ^ 4 CH 2 C ^ 5 ħ 4）。乙炔与二铁化合物，得到形式的Fe的乙烯基酮桥接衍生物光化学反应2（CO）（μ [-CO）μ - η 1：η 3 -RCC（R）CO]（μ - η 5，η 5 -C 5 H 4 CH 2 C 5 H4），其中R ＝ CH 3 O 2 C和C 6 H 5。钌的反应2（CO）4（μ - η 5，η 5 -C 5 H ^ 4 CH 2 C ^ 5 ħ 4与三苯基膦在光化学条件导致两个碳的损失一氧化碳配位体NADPC插入由钌到产率）
• Reactions of Doubly Bridged Bis(cyclopentadienes) with Iron Pentacarbonyl
  作者：Baiquan Wang、Bolin Zhu、Jianyong Zhang、Shansheng Xu、Xiuzhong Zhou、Linhong Weng

  DOI：10.1021/om030364a

  日期：2003.12.1

  diiron complexes (Me2C)(Me2E)[(η5-t-BuC5H2)Fe(CO)2]2 (E = Si(10), Ge (13)) and (Me2C)(Ph2Si)[(η5-C5H3)Fe(CO)2]2 (15) were obtained, in addition to the desilylation or degermylation products. When a methylene bridge was used instead of an isopropylene bridge in 1 and 6, the partially hydrogenated complexes (Me2E)(η3-CHC5H6)(η5-C5H3)Fe(CO)3Fe(CO)2 (E = Si (24), Ge (28)), the diiron complexes (CH2)(M

  当双桥双（环戊二烯）配体（Me 2 C）（Me 2 Si）（C 5 H 4）2（1）与Fe（CO）5在回流的甲苯中反应时，异常产物[（C 5 H 6） （ME 2 C）（ME 2 Si）的（η 5 -C 5 H ^ 3）的Fe（CO）] 2（μ-CO）2（2）用氢化双键的环戊二烯配位体之一，二铁络合物（箱2 C）（ME 2 Si）的[（η 5 -C 5 H ^3）Fe（CO）2 ] 2（3），得到甲硅烷基化产物4。当在回流的二甲苯中进行的反应中，新的复杂的（ME 2 C）（η 5 -C 5 H ^ 3）（η 5：η 1 -C 5 ħ 3）[（ME 2 Si）的铁（CO）2 ]的[Fe（CO）2 ]（5）与一种Fe-Si键，这应通过在配体的C-Si键的裂解相伴，除了分离的配合物2〜4。当使用与R 2 C（R 2 C = Me 2 C，（CH 2）5 C）和Me 2 E（E = Si，Ge）基
• Synthese und strukturelle charakterisierung von bcpm-Metallcarbonyl-Dimeren (bcpm = Biscyclopentadienylmethan) mit metallen der 6. nebengruppe
  作者：Henri Brunner、Roland Graßl、Joachim Wachter、Bernd Nuber、Manfred L. Ziegler

  DOI：10.1016/0022-328x(92)80113-c

  日期：1992.6

  The reaction of methylendicyclopentadiene (bcpmH2) with (CH3CN)3M(CO)3 (M  Cr, Mo, W) gives the complexes bcpmM2(CO)6 (1–3) in good yields (47–78%). The synthesis of bcpmMo2(CO)6Cl2 (4) starts from bcpmLi2 and Mo(CO)6. In a one-pot procedure, acidification with CH3CO2H and reaction with CCl4 give 4 in 43% yield. Low temperature 1H NMR investigations of 1 and 2 reveal a dynamic process analogous to

  methylendicyclopentadiene的（bcpmH反应2）以（CH 3 CN）3 M（CO）3（M铬，钼，W）给出络合物bcpmM2（CO）6（1-3）以良好的收率（47-78％ ）。bcpmMo 2（CO）6 Cl 2（4）的合成从bcpmLi 2和Mo（CO）6开始。在一锅法中，用CH 3 CO 2 H酸化并与CCl 4反应，得到4的产率为43％。1和2的低温1 H NMR研究揭示了一种动态过程，该过程类似于已针对甲硅烷基桥接的同系物观察到的过程。X射线分析1证明了分子的手性结构，这是bcpm-配体变形的结果。CrCr距离为3.211（2）Å。
• Koepf, Hartmut; Klouras, Nikolaos, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1983, vol. 38, # 3, p. 321 - 325
  作者：Koepf, Hartmut、Klouras, Nikolaos

  DOI：——

  日期：——