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

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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 Td 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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ACKNOWLEDGMENTS

The authors are grateful to D.V. Muratov for help in discussion of the results and to A.S. Peregudov for recording NMR spectra. The XRD studies were carried out using the equipment of the JRC PMR IGIC RAS.

Funding

This work was carried out in the framework of the state assignment no. 075-03-2023-642 (Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences) by the Ministry of Science and Higher Education of the Russian Federation. The theoretical part of the work was supported by the Ministry of Science and Higher Education of the Russian Federation as a part of the state assignment of the Kurnakov Institute of General and Inorganic Chemistry (Russian Academy of Sciences).

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Authors and Affiliations

  1. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia

    S. V. Osintseva & O. V. Semeikin

  2. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia

    F. M. Dolgushin & I. V. Anan’ev

  3. National Research University Higher School of Economics, Moscow, Russia

    E. D. Tselukovskaya & I. V. Anan’ev

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  1. S. V. Osintseva
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  2. O. V. Semeikin
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  3. F. M. Dolgushin
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Correspondence to F. M. Dolgushin.

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Translated by E. Yablonskaya

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Osintseva, S.V., Semeikin, O.V., Dolgushin, F.M. et al. Synthesis and Specific Features of the Molecular and Crystal Structures of Cp4Ru4(µ3-CO)4 Cluster. Russ J Coord Chem 49, 830–840 (2023). https://doi.org/10.1134/S1070328423600249

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  • DOI: https://doi.org/10.1134/S1070328423600249

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