University of Konstanz , Department of Chemistry , Universitätsstraße 10 , 78457 Konstanz , Germany.
Inorg Chem. 2019 Feb 18;58(4):2695-2707. doi: 10.1021/acs.inorgchem.8b03253. Epub 2019 Feb 7.
Ruthenocene-vinylruthenium conjugates Rc/Rc*-CH═CH-Ru(CO)(L)(P Pr) (Rc = (η-CH)Ru(η-CH); Rc* = (η-CMe)Ru(η-CH); L = Cl or κ O, O' -acetylacetonato) have been prepared and investigated in their neutral, mono-, and dioxidized states by cyclic voltammetry, IR and UV/vis/NIR spectroelectrochemistry, and EPR spectroscopy. Their corresponding radical cations are (almost) completely delocalized mixed-valent systems as indicated by the low half-widths, the absence of solvatochromism, and the low-energy cutoff of their IVCT bands in the near-infrared (NIR) and their IR and EPR 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, Δ E, in the ruthenocene congeners. All experimental results are backed by quantum chemical calculations.
钌翁-乙烯钌配合物 Rc/Rc*-CH═CH-Ru(CO)(L)(P Pr)（Rc = (η-CH)Ru(η-CH)；Rc* = (η-CMe)Ru(η-CH)；L = Cl 或 κ O,O' -乙酰丙酮酸根）已通过循环伏安法、红外和紫外/可见/近红外光谱电化学以及电子顺磁共振波谱法在其中性、单氧化态和双氧化态下进行了研究。其相应的自由基阳离子是（几乎）完全离域的混合价体系，这表现在低半峰宽、无溶剂变色性以及近红外（NIR）和它们的红外和电子顺磁共振波谱特征中的 IVCT 带的低能量截止。尽管乙烯钌和金属茂基实体之间的固有半波电势存在可比性差异，而且在钌翁同系物中半波电势分裂，Δ E 也大大减小，但电子耦合程度甚至超过了它们的二茂铁类似物。所有实验结果都得到了量子化学计算的支持。
