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

在此之前，我们已经报道了一些双核鲁新世衍生物采用EEC类型的氧化还原过程，并得到了稳定的氧化产物作为可分离的晶体，尽管鲁新世本身经历了不可逆的e-氧化。最近的研究结果表明，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、桥接配体的种类等不同，在任何一种有限结构上都可以发生不同的反应。例如，先前报道的（μ-η^6, η^6-fulvalene）二钌配合物与腈反应生成Ru (II)-Ru （IV）混价配合物，与溴反应生成Ru (IV)-Ru （IV）配合物。在噻吩-桥接双核钌烯二世衍生物的氧化反应中，没有得到稳定的氧化物质，但氧化物质与腈反应得到稳定的Ru (II)-Ru （IV）衍生物。Soc。日本,2000)。然而，在由噻吩[3,2 -b]桥接的双核钌二世衍生物的氧化过程中，分离出一种稳定的Ru (II)-Ru （II）型配合物，并与腈反应生成Ru (II)-Ru （IV）配合物（第50届有机金属配合物研讨会，2000）。结合不饱和化合物桥接的双核钌烯衍生物，研究了同环桥接的双核钌烯衍生物的合成。结果表明，可以制备出（μ-η^5， η^5-茚二烯- 4,8 -二酮）包封的双核钌配合物。在化合物的质子化过程中，羰基被质子化但没有转化为羟基，正电荷几乎定位在氧原子上。这种质子化很少被报道。所得配合物的结构通过x射线衍射测定。由于μ-η^5， η^5-茚二烯- 4,8 -二酮配体被迫呈平面结构，我们认为α-钌二烯阳离子部分不能呈稳定的氟烯结构。Soc。日本,2001)。少

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