1,1'-bis[(trimethylsilyl)ethynyl]ruthenocene | 158404-33-2

• 英文名称: 1,1'-bis[(trimethylsilyl)ethynyl]ruthenocene
• 英文别名: 1,1'-(Me3SiCCC5H4)2Ru；[Ru(η-C5H4CSiMe3)2]
• CAS: 158404-33-2
• 化学式: C₂₀H₂₆RuSi₂
• 分子量: 423.667
• InChiKey: KCRVCIDFPATKDU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1,1'-bis[(trimethylsilyl)ethynyl]ruthenocene 在 KOH 、 CH₃OH 作用下， 以 甲醇 、 乙醚 、 水 为溶剂， 以74%的产率得到1,1'-(1-methoxy-1,3-butadienylene)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
• 作为产物：
  描述：

  1,1'-diiodoruthenocene 、 三甲基乙炔基硅 在 catalyst: mixt. of PdCl₂(PPh₃)2 and Cu(OAc)2*H₂O 作用下， 以 further solvent(s) 为溶剂， 以69%的产率得到1,1'-bis[(trimethylsilyl)ethynyl]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

文献信息

• Phosphine-gold(I) derivatives of 1,1′-bis(alkynyl)metallocenes: Molecular structures of Fc’(CCX)2 [X = Au(PPh3), SiMe3] and Au4{(CC)2Fc’}2(PPh3)2 [Fc’ = Fe(η-C5H4-)2]
  作者：Michael I. Bruce、Martyn Jevric、Brian W. Skelton、Allan H. White、Natasha N. Zaitseva

  DOI：10.1016/j.jorganchem.2010.04.026

  日期：2010.7

  Desilylation of Fc'(C = CSiMe3) 2 [1; Fc' Fe(eta-C5H4-)(2)] with LiMe or KOH/MeOH, followed by addition of AuCl(PR3), afforded Fc'C = CAu(PR3)}(2) [R = Ph 2a, tol 2b]; the Ru analogue of 2a was also prepared. The XRD structures of 1 and 2a are reported. In the presence of CuI, a similar reaction over 2 h afforded the Au-4 cluster Au-4(C = C)(2)Fc'}(2)(PPh3)(2) 3. The X-ray determined structure of 3 showed a planar centrosymmetric Au-4 rhomb, two opposed Au atoms being sigma-bonded to the C = C group, while the other two Au atoms are each eta(2)-bonded to the C = C group and a PPh3 ligand. (C) 2010 Elsevier B. V. All rights reserved.
• Trimetallic complexes containing 1,1′-Rc′(CC)2 units [Rc′=ruthenocene-1,1′-diyl, Ru(η-C5H4–)2]
  作者：Michael I. Bruce、Martyn Jevric、Gary J. Perkins、Brian W. Skelton、Allan H. White

  DOI：10.1016/j.jorganchem.2006.11.037

  日期：2007.3

  Reactions between 1,1'-(Me3SiC equivalent to C)(2)Rc' [Rc' = ruthenocen-1, 1'-diyl, Ru(eta-C5H4-)(2)] and RuCl(PP)Cp' in the presence of KF gave 1,1'-Cp(PP)RuC equivalent to C}(2)Rc' [Cp' = CP, PP = PPh3 1, P(m-tol)(3) 2, dppe 3, dppf 4; Cp' = Cp*, PP = dppe 5]. Compounds 1 and 2 react with tcne to give two diastereomers a/b of the allylic (vinylcarbene) complexes 6 and 7, while methylation of 5 gave the bis-vinylidene [1,1'-Cp*(dppe)Ru=C=CMe}2Rc'](BPh4)(2) (8). The X-ray structures of 4, 6b and 8 have been determined. Cyclic voltammograms indicate that there is some electronic communication between the ruthenium end-groups through the Rc' centre. (c) 2006 Elsevier B.V. All rights reserved.