1-ethynyl-1′,2′,3′,4′,5′-pentamethylruthenocene | 188579-99-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: 1-ethynyl-1′,2′,3′,4′,5′-pentamethylruthenocene
• 英文别名: 1',2',3',4',5'-pentamethylruthenocenyl-ethyne；1-ethynyl-1',2',3',4',5'-pentamethylruthenocene；(pentamethylruthenocenyl)acetylene；5-ethynylcyclopenta-1,3-diene;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;ruthenium(2+)
• CAS: 188579-99-9
• 化学式: C₁₇H₂₀Ru
• 分子量: 325.416
• InChiKey: JRYKKXRWTYXCDG-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：

  五甲基环戊二烯基双(三苯基膦)氯化钌(II) 、 1-ethynyl-1′,2′,3′,4′,5′-pentamethylruthenocene 以 1,4-二氧六环 、 水 为溶剂， 以49%的产率得到(η(5)-C5Me5)Ru(η(5)-C5H4CC)Ru(PPh3)2(η(5)-C5Me5)
  参考文献：
  名称：

  Novel Structural Rearrangements Induced by Metal−Metal Interactions in Ruthenium(II) Ruthenocenyl- and (Pentamethylruthenocenyl)acetylide Complexes, RcC⋮CRuL₂(η⁵-C₅R₅) and Rc‘C⋮CRuL₂(η⁵-C₅R₅) [Rc = Ruthenocenyl, Rc‘ = Pentamethylruthenocenyl, L₂ = 2PPh₃ or Ph₂PCH₂CH₂PPh₂ (dppe), R = H or Me]

  摘要：

  The reaction of RcC=CH [Rc = (eta(5)-C5H5)Ru(eta(5)-C5H4)] with RuClL2(eta(5)-C5R5) [R = H or Me; L-2 = 2PPh(3) or Ph2PCH2CH2PPh2 (dppe)] in the presence of NH4PF6 and subsequent treatment with base gave Ru(II) ruthenocenylacetylide complexes RcC=CRuL2(eta(5)-C5R5) in good yields. In a similar manner, the pentamethylruthenocene analogues, Rc'C=CRuL2(eta(5)-C5R5) [Rc' = (eta(5)-C5Me5)Ru(eta(5)-C5H4)], were also prepared. Cyclic voltammograms of the complexes showed two reversible one-electron-oxidation processes, consisting of the processes [Ru(II)Ru'(II)] to [Ru(III)Ru'(II)] and then to [Ru(III)Ru(III)]. Chemical oxidation of the complexes induced novel structural rearrangement. The two-electron oxidation of complex RcC=CRu(PPh3)(2)(eta(5)-C5H5) afforded a kind of allenylidene complex, a cyclopentadienylidenethylidene complex, [(eta(5)-C5H5)Ru{mu-eta(6):eta(1)-C5H4C=C}Ru(PPh3)(2)(eta(5)-C5H5)](2+), in 90% yield. The one-electron oxidation of Rc'C=CRu(PPh3)(2)(eta(5)-C5H5) gave the vinylidene complex (Rc'CH=C)Ru(PPh3)(2)(eta(5)-C5H5) in 62% yield, while the two-electron oxidation led to the fulvene-vinylidene complex [(eta(6)-C5Me4CH2)Ru{mu-eta(5):eta(1)-C5H4CH=C}Ru(PPh3)(2)(eta(5)-C5R5)](2+) by an intramolecular hydrogen transfer in 59% yield.

  DOI：

  10.1021/om960732t
• 作为产物：
  描述：

  1-(α-chloro-β-formylvinyl)-1',2',3',4',5'-pentamethylruthenocene 在 NaOH 作用下， 以 1,4-二氧六环 、 水 为溶剂， 以91%的产率得到1-ethynyl-1′,2′,3′,4′,5′-pentamethylruthenocene
  参考文献：
  名称：

  Novel Structural Rearrangements Induced by Metal−Metal Interactions in Ruthenium(II) Ruthenocenyl- and (Pentamethylruthenocenyl)acetylide Complexes, RcC⋮CRuL₂(η⁵-C₅R₅) and Rc‘C⋮CRuL₂(η⁵-C₅R₅) [Rc = Ruthenocenyl, Rc‘ = Pentamethylruthenocenyl, L₂ = 2PPh₃ or Ph₂PCH₂CH₂PPh₂ (dppe), R = H or Me]

  摘要：

  The reaction of RcC=CH [Rc = (eta(5)-C5H5)Ru(eta(5)-C5H4)] with RuClL2(eta(5)-C5R5) [R = H or Me; L-2 = 2PPh(3) or Ph2PCH2CH2PPh2 (dppe)] in the presence of NH4PF6 and subsequent treatment with base gave Ru(II) ruthenocenylacetylide complexes RcC=CRuL2(eta(5)-C5R5) in good yields. In a similar manner, the pentamethylruthenocene analogues, Rc'C=CRuL2(eta(5)-C5R5) [Rc' = (eta(5)-C5Me5)Ru(eta(5)-C5H4)], were also prepared. Cyclic voltammograms of the complexes showed two reversible one-electron-oxidation processes, consisting of the processes [Ru(II)Ru'(II)] to [Ru(III)Ru'(II)] and then to [Ru(III)Ru(III)]. Chemical oxidation of the complexes induced novel structural rearrangement. The two-electron oxidation of complex RcC=CRu(PPh3)(2)(eta(5)-C5H5) afforded a kind of allenylidene complex, a cyclopentadienylidenethylidene complex, [(eta(5)-C5H5)Ru{mu-eta(6):eta(1)-C5H4C=C}Ru(PPh3)(2)(eta(5)-C5H5)](2+), in 90% yield. The one-electron oxidation of Rc'C=CRu(PPh3)(2)(eta(5)-C5H5) gave the vinylidene complex (Rc'CH=C)Ru(PPh3)(2)(eta(5)-C5H5) in 62% yield, while the two-electron oxidation led to the fulvene-vinylidene complex [(eta(6)-C5Me4CH2)Ru{mu-eta(5):eta(1)-C5H4CH=C}Ru(PPh3)(2)(eta(5)-C5R5)](2+) by an intramolecular hydrogen transfer in 59% yield.

  DOI：

  10.1021/om960732t

文献信息

• Mixed-Valent Ruthenocene–Vinylruthenium Conjugates: Valence Delocalization Despite Chemically Different Redox Sites
  作者：Christopher Hassenrück、André Mang、Rainer F. Winter

  DOI：10.1021/acs.inorgchem.8b03253

  日期：2019.2.18

  spectroscopic signatures. The degree of electronic coupling even exceeds that of their ferrocene analogs despite comparable differences between the intrinsic half-wave potentials of the vinylruthenium and the metallocenyl entities and substantially smaller half-wave potential splittings, ΔE1/2, in the ruthenocene congeners. All experimental results are backed by quantum chemical calculations.

  茂钌-vinylruthenium缀合物RC / RC * -CH = CH-的Ru（CO）（L）（P我镨3）2（RC =（η 5 -C 5 H ^ 5）的Ru（η 5 -C 5 H ^ 4）; RC * =（η 5 -C 5我5）的Ru（η 5 -C 5 H ^ 4）; L = Cl或κ ø，ö ' -制备了乙炔基丙酮酸酯并通过循环伏安法，IR和UV / vis / NIR光谱电化学和EPR光谱研究了它们的中性，单氧化和双氧化状态。它们对应的自由基阳离子是（几乎）完全离域的混合价体系，如低半宽度，不存在溶剂变色现象以及它们的IVCT谱带在近红外（NIR）和IR和IR和EPR光谱签名。尽管乙烯基钌和金属茂基实体的固有半波电势之间的可比差异以及明显较小的半波电势分裂ΔE 1/2，但电子耦合程度甚至超过了二茂铁类似物的电耦合程度。，在钌茂金属同类物中。所有实验结果均得到量子化学计算的支持。
• Synthesis and Redox Behavior of Ruthenium(II) 2,3,4,5-Tetramethylruthenocenylacetylide and Related Complexes. Formation of μ-η⁶:η¹-[(Cyclopentadienylidene)ethylidene]diruthenium Complexes Containing a Strong Metal−Metal Interaction
  作者：Masaru Sato、Ayako Iwai、Masanobu Watanabe

  DOI：10.1021/om990138u

  日期：1999.8.1

  Ru(C⋮CRc)(dppe)(η5-C9H7), and Ru(C⋮CRc‘)(dppe)(η5-C9H7) were determined by X-ray analysis. Cyclic voltammetry of the acetylide complexes showed two well-separated quasi-reversible waves. Chemical oxidation of ruthenium(II) 2,3,4,5-tetramethylruthenocenylacetylide complexes gave products whose stability was dependent on the ligand on the Ru(II) moiety. The 13C NMR spectrum of the oxidized species isolated

  通过1-甲酰基-2,3,4,5-四甲基钌茂与三甲基甲硅烷基重氮甲基锂的反应以及1-（2'，2'-二氯乙烯基）的反应制备1-乙炔基-2,3,4,5-四甲基钌茂铁）-2,3,4,5-四甲基钌茂金属，其是由1-甲酰基-2,3,4,5-四甲基钌茂金属与二氯甲基二乙基膦酸锂和叔丁基锂反应制得的。1-乙炔基-2,3,4,5- tetramethylruthenocene用的RuCl反应P 2 L（P 2 = 2 PPH 3或DPPE; L =η-C 5 H ^ 5， η-C 5我5，或η 5 -C 9高7）在NH 3的存在下4 PF 6或的AgBF 4，随后柱层析上停用的Al 2 ö 3，得到的Ru（C⋮CRC'）P 2 L的中度或良好的产率。茹（C⋮CRC）P 2（η 5 -C 9 ħ 7）和Ru（C⋮CRC *）P 2（η 5 -C 9 ħ 7）类似地制备（RC中，R c”，和R c *是ruthenocenyl
• A facile structural rearrangement to unprecedented µ2-η6:η6-bis(cyclopentadienylidene)ethene diruthenium complexes in the oxidation of 1,2-bis(ruthenocenyl)ethynesElectronic supplementary information (ESI) available: elemental analysis, 1H and 13C NMR, IR and Raman spectra. See http://www.rsc.org/suppdata/cc/b2/b202811p/
  作者：Masaru Sato、Masanobu Watanabe

  DOI：10.1039/b202811p

  日期：2002.7.11

  The two-electron oxidation of 1,2-bis(ruthenocenyl)ethynes and bis(1′,2′,3′,4′,5′-pentamethylruthenocenyl)ethynes, prepared from alkyne metathesis of the corresponding propynes, gave the unprecedented μ2-η6:η6-bis(cyclopentadienylidene)ethene diruthenium complexes.

  1,2-双(二茂钌基)乙炔和双(1,2,3,4,5-五甲基二茂钌基)乙炔的二电子氧化，由相应的丙炔的炔烃复分解反应制备，得到了前所未有的μ2-μ6:μ6-双(环戊二烯)乙烯二钌配合物。