1,1'-(1-butenylene)ruthenocene | 158404-37-6

• 英文名称: 1,1'-(1-butenylene)ruthenocene
• CAS: 158404-37-6
• 化学式: C₁₄H₁₄Ru
• 分子量: 283.335
• InChiKey: LRVZIGMZBNRHQX-JIBDQCPFSA-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：

  1,1'-(4-oxo-1-butenylene)ruthenocene 在 AlCl₃ 、 LiAlH₄ 作用下， 以 乙醚 为溶剂， 以97%的产率得到1,1'-(1-butenylene)ruthenocene
  参考文献：
  名称：

  Structure, Reactivity, and Electronic Properties of [4]Ferrocenophanes and [4]Ruthenocenophanes Prepared via a Novel Heteroannular Cyclization Reaction

  摘要：

  The reactions of 1,1'-bis((trimethylsilyl)ethynyl)ferrocene and 1,1'-bis((trimethylsilyl)-ethynyl)ruthenocene with catalytic quantities of alkali-metal methoxides in methanol directly afforded the highly unsaturated [4]metallocenophanes 1,1'-(1-methoxy-1,3-butadienylene)-ferrocene and 1,1'-(1-methoxy-1,3-butadienylene)ruthenocene, respectively, in high yields via a novel desilylation/heteroannular cyclization sequence. Analogously, 1,1'-bis((trimeth-ylsilyl)ethynyl)octamethylferrocene reacted to give 1,1'-(1-methoxy-1,3-butadienylene)oc-tamethylferrocene in high yield. The reactions of ((trimethylsilyl)ethynyl)ferrocene and ((trimethylsilyl)ethynyl)ruthenocene under identical conditions afforded ethynylferrocene and ethynylruthenocene, respectively. Synthetic elaboration of the heteroannular bridge of the cyclization products provided a route to additional [4]metallocenophanes. Treatment of 1,1'-(1-methoxy-1,3-butadienylene)ferrocene with acidic silica gel afforded 1,1'-(4-oxo-1-butenylene)ferrocene. Reaction of 1,1'-(4-oxo-1-butenylene)ferrocene with alane provided 1,1'-(1-butenylene)ferrocene, while reaction with sodium borohydride gave 1,1'-(4-hydroxy-1-butenylene)ferrocene. Dehydration of 1,1'-(4-hydroxy-1-butenylene)ferrocene on activated alumina provided 1,1'-(1,3-butadienylene)ferrocene. Similar synthetic transformations were carried out to yield the analogous series of ruthenocenophanes and octamethylferro-cenophanes. Voltammetric half-wave oxidation potentials were measured for all of the metallocenophanes in order to evaluate the electronic effect of the heteroannular bridges. X-ray crystal structure analyses were carried out on 1-1'-(1-methoxy-1,3-butadienylene)-ferrocene and 1,1'-(1-methoxy-1,3-butadienylene)ruthenocene. 1,1'-(1-Methoxy-1,3-butadi-enylene)ferrocene, C15H14FeO, crystallized in the orthorhombic space group Pcnb with a = 26.997(5) angstrom, b = 5.981(2) angstrom, c = 28.962(3) angstrom, Z = 16, and R = 0.072. 1,1'-(1-Methoxy-1,3-butadienylene)ruthenocene, C15H14RuO, crystallized in the monoclinic C2/c space group with a = 20.590(3) angstrom, b = 9.023(2) angstrom, c = 13.940(2) angstrom, 111.296(8)-degrees, Z = 8, and R = 0.021.

  DOI：

  10.1021/om00020a026