Study for the Novel Metal-metal Interaction in the Binuclear Ruthenocene Derivatives

双核钌茂衍生物中新型金属-金属相互作用的研究

• 批准号: 10640538
• 负责人: SATO Masatu
• 金额: $ 1.92万
• 依托单位: Saitama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640538/
• 关键词: Ruthenocene; Binuclear Transition Metal Complex; 2-electron oxidation; Metal-metal Interaction; 2核遷移金属 錯体

Previously, we have reported that some of the binuclear ruthenocene derivatives took an EEC type of redox process and gave a stable oxidized species as isolable crystals, although ruthenocene itself underwent an irreversible 2e-oxidation. As a recent result, it became clear that there is a resonance of the limited structures among Ru (II)-Ru (II), Ru (III)-Ru (III), and Ru (II)-Ru (IV), and various reactions take place from either of the limited structure according to the total structure of the molecule, the kind of the bridging ligand, and so on. For example, the previouslyreported (μ-η^6, η^6-fulvalene) diruthenium complex reacted with nitriles to give a Ru (II)-Ru (IV) mixed-valence complex and with bromine to give Ru (IV)-Ru (IV) complex through the Ru (II)-Ru (IV) state. In the oxidation of the thiophene-bridsing binuclear ruthenocene derivatives, no stable oxidizing species was obtained, but the reaction of the oxidizing species with nitriles gave a stable Ru (II)-Ru (IV) derivat … More ive (78th Annual Meeting of Chem. Soc. Jpn, 2000). However, in the oxidation of binuclear ruthenocene derivatives bridged by the thieno [3, 2-b] thiophene, a stable Ru (II)-Ru (II) type of complex was isolated and the reaction of it with nitrile afforded the Ru (II)-Ru (IV) complex (50th Symposium on Organometllic Complex, 2000).In connection with the binuclear ruthenocene derivatives bridged by an unsaturated compound, the synthesis of the homoannnularly bridged binuclear ruthenocene derivatives was examined. As the result, the (μ-η^5, η^5-indacene-4, 8-dione)-buridging binuclear Ru complexes could be prepared. In the protonation of the compouns, the carbonyl group was protonated but not be converted to a hydroxyl group and the positive charge is almost localized on the oxygen atom. Such protonation is rarely reported. The structure of the resulting dication complex was determined by X-ray diffraction. We think that the α-ruthenocenium cation part cannot take a stabe fulvene structure, because the μ-η^5, η^5-indacene-4, 8-dione ligand is forced to take the planar structure (78th Annual Meeting of Chem. Soc. Jpn, 2001). Less

此前，我们报道过一些双核钌茂衍生物采用EEC类型的氧化还原过程，并以可分离晶体的形式产生稳定的氧化物质，尽管钌茂本身经历了不可逆的2e氧化。最近的结果表明，存在这种情况。 Ru (II)-Ru (II)、Ru (III)-Ru (III) 和 Ru (II)-Ru (IV) 之间有限结构的共振以及各种反应根据分子的总结构、桥连配体的种类等，从有限结构中的任一个发生。例如，先前报道的(μ-η^6，η^6-富瓦烯)二钌络合物发生反应。与腈反应生成Ru(II)-Ru(IV)混合价络合物，与溴通过氧化反应生成Ru(IV)-Ru(IV)络合物。在噻吩桥联双核钌茂衍生物中，没有获得稳定的氧化物质，但氧化物质与腈的反应得到了稳定的 Ru (II)-Ru (IV) 衍生物……更多 ive（第 78 届化学学会年会） Jpn，2000）然而，在噻吩桥联的双核钌茂衍生物的氧化中[3， 2-b]噻吩，一种稳定的 Ru (II)-Ru (II) 型络合物被分离出来，它与腈反应得到 Ru (II)-Ru (IV) 络合物（第 50 届有机金属络合物研讨会，2000 年）结合不饱和化合物桥联的双核钌茂衍生物，研究了同环桥联的双核钌茂衍生物As的合成。结果，可以制备出(μ-η^5, η^5-indacene-4, 8-dione)-嵌合双核Ru配合物。在化合物的质子化过程中，羰基被质子化，但没有转化为α。羟基基团和正电荷几乎集中在氧原子上，这种质子化很少被报道，我们认为通过X射线衍射确定了所得的双阳离子配合物的结构。 α-钌茂鎓阳离子部分不能采取稳定的富烯结构，因为μ-η^5, η^5-indacene-4, 8-dione配体被迫采取平面结构（第78届日本化学会年会， 2001).更少

项目成果

M.SATO,et al: "Molecular structures of some syn-〔1.1〕metallocenophanes,anti-" Bull.Chem.Soc.Jpn.71. 2127-2136 (1998)

M.SATO 等人：“一些顺式-[1.1]金属茂烯芬烷的分子结构，反式”Bull.Chem.Soc.Jpn.71 (1998)。

Masaru SATO,et al: "Synnthesis,structure,and redox chemistry of 1,2-bis(ruthen…・" J.Chem.Soc.Dalton.Trans.2215-2224 (1998)

Masaru SATO 等人：“1,2-bis(ruthen...的合成、结构和氧化还原化学”J.Chem.Soc.Dalton.Trans.2215-2224 (1998)

M. WATANABE, M. SATO: "A novel coordination mode of the fulvalene ligand in binuclear・・・"Organometallics. 18. 2127-2136 (1999)

M. WATANABE、M. SATO：“双核中富瓦烯配体的新型配位模式......”有机金属学。 18. 2127-2136 (1999)

M. SATO, et al.: "Synthesis and redox Behavior of ruthenium 2,3,4,5-tetramethyl・・・"Organometallics. 18. 3208-3219 (1999)

M. SATO 等人：“2,3,4,5-四甲基钌的合成和氧化还原行为”有机金属学。18. 3208-3219 (1999)