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
基本信息
- 批准号:10640538
- 负责人:
- 金额:$ 1.92万
- 依托单位:
- 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:
- 关键词:
项目摘要
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
以前,我们已经报道,一些双核茂衍生物采取了EEC型的氧化还原过程,并给出了一个稳定的氧化物种作为可分离的晶体,虽然茂本身经历了不可逆的2 e-氧化。作为最近的结果,变得清楚的是,在Ru(II)-Ru(II)、Ru(III)-Ru(III)和Ru(II)-Ru(IV)之间存在有限结构的共振,并且根据分子的总结构、桥接配体的种类等,从有限结构中的任一个发生各种反应。(μ-η^6,η^6-富瓦烯)二钌配合物与腈反应生成Ru(II)-Ru(IV)混合价配合物,与溴反应生成Ru(II)-Ru(IV)混合价配合物。在噻吩桥联的双核茂钌衍生物的氧化反应中,没有得到稳定的氧化物种,但氧化物种与腈反应得到稳定的Ru(II)-Ru(IV)衍生物, ...更多信息 Ive(第78届日本化学会年会,2000)。而在以噻吩并[3,2-B]噻吩为桥的双核二茂茂衍生物的氧化反应中,分离出稳定的Ru(II)-Ru(II)型配合物,并将其与腈反应得到Ru(II)-Ru(IV(第50届有机金属络合物研讨会,2000年)。关于由不饱和化合物桥连的双核二茂衍生物,研究了同环桥联的双核并茂衍生物的合成。结果表明,可以合成(μ-η^5,η^5-引达省-4,8-二酮)-嵌段双核钌配合物.在质子化反应中,羰基被质子化,但没有转化为羟基,正电荷几乎集中在氧原子上。这样的质子化很少报道。用X-射线衍射法测定了配合物的结构。我们认为α-二茂阳离子部分不能形成稳定的富烯结构,因为μ-η^5,η^5-引达省-4,8-二酮配体被迫形成平面结构(第78届日本化学会年会,2001)。少
项目成果
期刊论文数量(4)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
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)。
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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)
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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)
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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)
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