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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >[Cp*Ru(s-indacene)RuCp*] and [Cp*Ru(s-indacene)RuCp*]+: Experimental and theoretical findings concerning the electronic structure of neutral and mixed valence organometallic systems
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[Cp*Ru(s-indacene)RuCp*] and [Cp*Ru(s-indacene)RuCp*]+: Experimental and theoretical findings concerning the electronic structure of neutral and mixed valence organometallic systems

机译：[Cp * Ru（s-indacene）RuCp *]和[Cp * Ru（s-indacene）RuCp *] +：关于中性和混合价有机金属体系电子结构的实验和理论发现

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摘要

The reaction of 2,6-diethyl-4,8-dimethyl-s-indacenyl-dilithium (Li2Ic0) with [Cp*RuCl]4 gives the organometallic binuclear bis-pentamethylcyclopentadienyl-ruthenium-s-indacene complex, [{Cp*Ru}2Ic0] (1, Ic0 = 2,4-diethyl-4,8-dimethyl-s-indacene), in high yields. The subsequent oxidation of 1 with a ferricinium salt ([Fc]+[BF4]) gives the mixed valence compound [{Cp*Ru}2Ic0]+[BF4] (1+). Compound 1 was structurally characterized by X-ray crystallography, finding that both {Cp*Ru} fragments are coordinated to opposite sites of the Ic0 ligand. The structural and electronic features of 1 and 1+ have been rationalized by Density Functional Theory (DFT) calculations, which suggest that both metallic centers get closer to the Ic0 and subtle electronic reorganizations occurs when chemical oxidation takes place. Cyclic voltammetry and ESR experiments suggest a high electronic interaction between the metallic centers mediated by the Ic0 bridging ligand. Time dependent DFT (TD-DFT) calculations were carried out to understand and assign the intervalence band present in the mixed-valent specie (1+). The main achievement of this article is to feature the relationship of the experimental data with the computational results obtained with the Amsterdam Density Functional package (ADF). Both experimental and theoretical facts demonstrate that the mixed valence system (1+) is a delocalized one, and it can be classified as a Class III system according to the Robin & Day classification.
机译：2，6-二乙基-4,8-​​二甲基-s-茚并茚基-二锂（Li2Ic0）与[Cp * RuCl] 4的反应得到有机金属双核双五甲基环戊二烯基-钌-s-茚并茂络合物，[{Cp * Ru } 2Ic0]（1，Ic0 = 2,4-二乙基-4,8-​​二甲基-s-茚并四烯），高收率。随后用铁盐（[Fc] + [BF4]）氧化1，得到混合化合价化合物[{Cp * Ru} 2Ic0] + [BF4]（1+）。通过X射线晶体学对化合物1进行结构表征，发现两个{Cp * Ru}片段均与Ic0配体的相反位点配位。 1和1+的结构和电子特征已通过密度泛函理论（DFT）计算进行了合理化，这表明两个金属中心都更靠近Ic0，并且在发生化学氧化时会发生微妙的电子重组。循环伏安法和ESR实验表明，由Ic0桥联配体介导的金属中心之间存在高电子相互作用。进行了与时间有关的DFT（TD-DFT）计算，以了解并指定存在于混合价种（1+）中的间隔带。本文的主要成就是将实验数据与通过阿姆斯特丹密度函数软件包（ADF）获得的计算结果之间的关系作为特征。实验和理论事实均表明，混合价系统（1+）是一个离域系统，根据Robin＆Day分类，它可以分类为III类系统。

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