Synthesis and Specific Features of the Molecular and Crystal Structures of Cp4Ru4(µ3-CO)4 Cluster

IF 16.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Accounts of Chemical Research Pub Date : 2023-12-19 DOI:10.1134/S1070328423600249

S. V. Osintseva, O. V. Semeikin, F. M. Dolgushin, E. D. Tselukovskaya, I. V. Anan’ev

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Abstract

Tetranuclear cluster [Ru(μ₃-CO)Cp]₄ (I) is synthesized as a minor product in the thermal reaction of cyclopentadiene with Ru₃(CO)₁₂ aimed at preparing ruthenium dimer [Ru(CO)₂Cp]₂. The spectral (¹³С and ¹H NMR, IR) and structural studies are carried out for cluster I. Under different conditions, the crystallization of cluster I gives dark cherry-colored crystals of two types: cluster Ia and its tetrahydrate Ib. The structures of compounds Ia and Ib are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2241197 and 2241199, respectively). A comparative analysis of the cluster geometry shows that the distortion of the Ru₄(CO)₄ cage in compound I from the ideal T_d symmetry in the structure of the pure compound is due to anisotropy of intermolecular contacts in the crystal. Specific features of chemical binding in the [Ru(μ₃-CO)Cp]₄ cluster and its iron-containing analog are studied by DFT calculations using topological analysis of the electron density comparing the energy characteristics and effective force constants of binding interactions. A necessity to use criteria of elastic deformations of interatomic interactions (force constants) for the correction description of such structural chemical phenomena as structural nonrigidity of the cage in transition metal clusters is demonstrated.

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Cp4Ru4(µ3-CO)4团簇的合成及其分子结构和晶体结构的具体特征

摘要四核团簇[Ru(μ3-CO)Cp]4 (I)是环戊二烯与 Ru3(CO)12 热反应的次要产物，目的是制备钌二聚体[Ru(CO)2Cp]2。对簇 I 进行了光谱（13С 和 1H NMR、IR）和结构研究。在不同条件下，簇 I 结晶出两种深樱桃色晶体：簇 Ia 及其四水合物 Ib。化合物 Ia 和 Ib 的结构是通过 X 射线衍射 (XRD) 确定的（CIF 文件 CCDC 编号分别为 2241197 和 2241199）。对化合物簇几何形状的比较分析表明，化合物 I 中的 Ru4(CO)4 笼与纯化合物结构中理想的 Td 对称性不同，是由于晶体中分子间接触的各向异性造成的。通过对电子密度进行拓扑分析，比较结合相互作用的能量特征和有效力常数，利用 DFT 计算研究了[Ru(μ3-CO)Cp]4 团簇及其含铁类似物中化学结合的具体特征。结果表明，有必要使用原子间相互作用的弹性变形标准（力常数）来校正描述过渡金属团簇中的笼结构非刚性等结构化学现象。

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来源期刊

Accounts of Chemical Research 化学-化学综合

CiteScore

31.40

自引率

1.10%

发文量

312

审稿时长

2 months

期刊介绍： Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.