1,4-bis(cymantrenyl)butadiyne | 12171-46-9

• 英文名称: 1,4-bis(cymantrenyl)butadiyne
• CAS: 12171-46-9
• 化学式: C₂₀H₈Mn₂O₆
• 分子量: 454.156
• InChiKey: IQVASADUAPMELN-UHFFFAOYSA-N

计算性质

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

• 作为产物：
  描述：

  (η5-HC2C5H4)Mn(CO)3 、 tricarbonyl(1,2-diethynylcyclopentadienyl)manganese 在 TMEDA 、 CuCl 作用下， 以 丙酮 为溶剂， 以8.2%的产率得到1,4-bis(cymantrenyl)butadiyne
  参考文献：
  名称：

  ortho- and meta-(Diethynylcyclopentadienyl)tricarbonylmanganese: Building Blocks toward the Construction of Metal Fragment Supported Fullerenynes?

  摘要：

  Starting from [(trimethylsilyl)ethynyl]cymantrene (1), the two isomeric 1,2- and 1,3-[bis-(trimethylsilyl)ethynyl]cymantrenes (3a, 4a) were prepared by a deprotonation/iodination/coupling sequence. The coupling reaction was performed on the mixed ortho-/meta-iodo[(trimethylsilyl)ethynyl]cymantrene (2) by using Stille methodology (tin alkynes and PdCl2(CH3CN)(2) as catalyst in ethyl ether/DMF). Separation of the isomers (3a, 4a) is achieved by chromatography over flash silica gel. The ortho-diethynylcymantrene 3a is isolated in 42%, while the corresponding meta compound 4a is formed in 26%. If the deprotonation reaction of 1 in pentane/TMEDA is performed under carefully controlled conditions (-78 degrees C), the formation of only ortho 2 is observed in 67% yield. Coupling with trimethylstannyl(trimethylsilyl)acetylene furnished 3a in 57%. Crystal structures have been carried out for complexes 3a (C2/c; a = 29.923(1), b = 15.9145(7), c = 9.327(1) Angstrom, alpha = 90, beta = 102.920(7), gamma = 90 degrees; V = 4329.1(6) Angstrom(3); Z = 8; 2948 reflections with F > 3 sigma(F); R = 0.071, R(w) = 0.074) and 4a (P2(1)2(1)2(1); a = 17.027(3), b = 12.339(4), c = 10.235(2) Angstrom; alpha = beta = gamma = 90 degrees; V = 2150(1) Angstrom(3); Z = 4; 1392 reflections with F > 3 sigma(F); R = 0.059, R(w) = 0.058), Removal of the alkyne-bound trimethylsilyl groups is achieved in yields of >80% by treatment of 3a and 4a with potassium carbonate in methanol. The parent diethynylcymantrenes (3b, 4b) are stable compounds. Treatment of 1,2-diethynylcymantrene 3b under Hay conditions gives coupled material, a polymer poly[(ortho-cymantrene)butadiynylene] (6) in 68% yield (M(n) = 9300). If the Hay reaction is conducted with 3b and an added capping reagent (ethynylcymantrene), a series of oligomeric butadiynylenecymantrenes is isolated starting from the dimer up to the heptamer (dimer 7a, 8.2%; trimer 7b, 12.5%; tetramer 7c, 7.7%; pentamer 7d, 5.5%; hexamer 7e, 3.6%; heptamer 7f, 2.5%; Sigma = 40%). The compounds were separated by chromatography over flash silica gel or preparative HPLC. The oligomers 7 are unstable lemon yellow powders.

  DOI：

  10.1021/om00005a053