deuterated pentamethylcyclopentadiene | 86677-57-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: deuterated pentamethylcyclopentadiene
• CAS: 86677-57-8
• 化学式: C₁₀H₁₆
• 分子量: 137.229
• InChiKey: WQIQNKQYEUMPBM-RAMDWTOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.31
• 重原子数：
  10.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  1,1-bis(4-methylphenyl)allene 、 deuterated pentamethylcyclopentadiene 在 2,6-二叔丁基吡啶 、 (CH₃C₆H₄)3NSbF₆ 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 0.12h， 以7%的产率得到1-[1-Deuterio-1-(4-methylphenyl)-2-(1,2,3,4,5-pentamethylcyclopenta-2,4-dien-1-yl)prop-2-enyl]-4-methylbenzene
  参考文献：
  名称：

  Cation Radical Catalyzed Diels-Alder Reaction of Electron-Rich Allenes

  摘要：

  The cation radical catalyzed cycloaddition of electron-rich arylallenes 1a-e with 1,2,3,4,5-pentamethylcyclopentadiene (2a) afforded the Diels-Alder products 3 and 4 at 0 degrees C in 5 min with a high chemoselectivity, facial selectivity, and stereoselectivity. From the results of various mechanistic tests, it is inferred that the electron transfer induced reaction proceeds via a [3 + 2] pathway by cycloaddition of the diene cation radical to a neutral allene 1 exhibiting a rather short chain length. However, with electron-withdrawing substituents at the remote end of the allene functionality, the cycloaddition is only a minor reaction path. With diarylallene 1f and diene 2a, or 2b, no cycloaddition but formation of products 7 and d(1)-7 occurred. It is concluded that distonic cation radicals may be intermediates in a stepwise formal Diels-Alder reaction induced by electron transfer.

  DOI：

  10.1021/jo00130a022
• 作为产物：
  描述：

  1,2,3,4,5-五甲基环戊二烯 在 sodium hydroxide 、 重水 作用下， 以 氘代二甲亚砜 为溶剂， 反应 0.08h， 生成 deuterated pentamethylcyclopentadiene
  参考文献：
  名称：

  羧酰胺取代四甲基环戊二烯——合成、表征及其铱（III）配合物催化亚胺还原

  摘要：

  新型二聚碘铱 ( III ) 配合物 [Ir(Cp*CONMe 2 )I 2 ] 2 , (Cp*CONMe 2 = η 5 - N,N -2,3,4,5-hexamethylcyclopenta-2,4 -diene carboxamide) 在四甲基环戊二烯环内带有酰胺部分，已被合成和表征。配体 Cp*CONMe 2被合成为两个区域异构体，但是由于围绕酰胺羰基碳和环碳的旋转受限，2-取代异构体作为两个可区分的构象异构体存在。Cp*CONMe 2和 Cp*的相对酸度通过它们的相对 H/D 交换率进行比较。N,N的铱络合物-2,3,4,5-hexamethylcyclopenta-2-4-diene carboxamide [IrCp*CONMe 2 ] 和 ( R,R )-1,2-diphenyl- N '-tosylethane-1,2-diamine (( R , R )-TsDPEN)

  DOI：

  10.1039/d2dt00149g

文献信息

• Halo- and alkyl(pentamethylcyclopentadienyl)[1,2-bis(diphenylphosphino)ethane]iron(III) 17-electron complexes: synthesis, NMR and magnetic properties and EHMO calculations
  作者：Christophe Roger、Paul Hamon、Loic Toupet、Hassan Rabaa、Jean Yves Saillard、Jean Rene Hamon、Claude Lapinte

  DOI：10.1021/om00050a041

  日期：1991.4

  Reaction of Fe(dppe)Cl2 (dppe = 1,2-bis(diphenylphosphino)ethane) with LiCp* (Cp* = eta-5-pentamethylcylopentadienyl) in THF yields Fe(Cp*)(dppe)Cl (1). The X-ray crystal structure of 1 shows that it crystallizes in the triclinic space group P1 with unit cell parameters a = 10.410(7) angstrom, b = 10.987(3) angstrom, c = 16.872 (4) angstrom, alpha = 80.43 (2)-degrees, beta = 94.28 (5)-degrees, gamma = 70.92 (5)-degrees, and Z = 2. The structure was solved and refined (5732 reflections) to the final residual values R = 0.37 and R(w) = 0.36. Compound 1 reacts with LiI and LiCH3 to afford respectively Fe(Cp*)(dppe)I (2) and Fe(Cp*)(dppe)CH3 (4). The hydride Fe-(Cp*)(dppe)H (3) can be obtained by reaction of 1 with LiAlH4 or by direct preparation in 50% yield from Cp*H and Fe(dppe)Cl2 reduced by a sonochemically (20 kHz) activated colloidal dispersion of potassium metal. The alkyl derivatives (Fe(Cp*)(dppe)R (R = CH3 (4) and CH2OCH3 (5)) are synthesized from FeCp*(CO)2R upon CO displacement by ultraviolet (UV) photolysis and trapping with dppe. Cyclic voltammetry (CV) reveals a reversible one-electron oxidation process for all these neutral iron(II) compounds including the hydride (3). Ferrocenium and trityl salts as well as molecular oxygen can be used to synthesize the halide and alkyl 17-electron [Fe(Cp*)(dppe)X]PF6 complexes in 90-95% yield. ESR, Mossbauer, and NMR experiments indicate that the Cp* ring and the alkyl or halide ligands contribute significantly to the delocalization of the odd electron. EHMO calculations on the [Fe(Cp)(PH3)2CH2OH].+ model are fully consistent with this finding: the singly occupied HOMO, of predominantly x2 - y2 character, is found to be 52% localized on the metal, 28% on Cp, and 15% on CH2OH. Magnetic susceptibility obeys the modified Curie-Weiss expression, and the important values of mu-B observed are attributed to an orbital contribution. The low and negative values observed for theta characterize these complexes as having short-distance dominant antiferromagnetic interactions.