[(2,3,4,5-tetramethylcyclopentadien-1-yl)ethynyl]trimethylsilane | 158357-76-7

• 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: [(2,3,4,5-tetramethylcyclopentadien-1-yl)ethynyl]trimethylsilane
• 英文别名: trimethyl-[2-(2,3,4,5-tetramethylcyclopenta-1,3-dien-1-yl)ethynyl]silane
• CAS: 158357-76-7
• 化学式: C₁₄H₂₂Si
• 分子量: 218.414
• InChiKey: VESDTRQFECSKLS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.17
• 重原子数：
  15.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  [(2,3,4,5-tetramethylcyclopentadien-1-yl)ethynyl]trimethylsilane 、 iron(II) chloride 在 BuLi 作用下， 以 四氢呋喃 、 正己烷 、 环己烷 为溶剂， 以59%的产率得到1,1'-bis[(trimethylsilyl)ethynyl]octamethylferrocene
  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
• 作为产物：
  描述：

  2,3,4,5-tetramethyl-1-(2-trimethylsilylethynyl)cyclopent-2-en-1-ol 以53%的产率得到
  参考文献：
  名称：

  Pudelski John K., Callstrom Matthew R., Organometallics, 13 (1994) N 8, S 3095-3109

  摘要：

  DOI：

文献信息

• Alkynyl Substitution and Linkage in Cobaltacarborane Sandwich Complexes
  作者：Dennis Malaba、Michal Sabat、Russell N. Grimes

  DOI：10.1002/1099-0682(200109)2001:10<2557::aid-ejic2557>3.0.co;2-h

  日期：2001.9

  diethynylphenylene connectors was explored by the synthesis of two classes of complexes in which the linking groups are attached to the Cp* ligands and to the carborane rings, respectively. Thus, the complex nido-(η5-C5Me4−C≡CH)Co(Et2C2B3H5) (6) was prepared and converted in 87% yield to the novel 1,4-diethynylphenylene-linked bis(metallacarborane) 1,4-[nido-(Et2C2B3H5)Co(η5-C5Me4−C≡C)]2C6H4 (7), which was

  Cp*Co(Et2C2B3H5) 夹心单元通过炔基和二乙炔基亚苯基连接器的连接是通过合成两类复合物来探索的，其中连接基团分别连接到 Cp* 配体和碳硼烷环。因此，制备了复合物 nido-(η5-C5Me4-C≡CH)Co(Et2C2B3H5) (6) 并以 87% 的产率转化为新型 1,4-二乙炔基亚苯基连接的双（金属碳硼烷）1,4-[nido -(Et2C2B3H5)Co(η5-C5Me4−C≡C)]2C6H4 (7)，通过多核 NMR 和质谱以及 X 射线晶体学表征。CuI 促进的 6 与过量二乙胺中的 (MeCN)2PdCl2 偶联用于制备钯衍生物，nido-(Et2C2B3H5)Co(C5Me4)-C≡C-Pd(NHEt2)2Cl (10)。第二种类型的复合物，其中有机接头直接连接到碳硼烷环上，