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

Tetranuclear cluster [Ru(μ 3 -CO)Cp] 4 (I) is synthesized as a minor product in the thermal reaction of cyclopentadiene with Ru 3 (CO) 12 aimed at preparing ruthenium dimer [Ru(CO) 2 Cp] 2 . The spectral ( 13 С and 1 H NMR, IR) and structural studies are carried out for cluster I. Under different co...

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Bibliographic Details
Published in:Russian journal of coordination chemistry 2023, Vol.49 (12), p.830-840
Main Authors: Osintseva, S. V., Semeikin, O. V., Dolgushin, F. M., Tselukovskaya, E. D., Anan’ev, I. V.
Format: Article
Language:English
Subjects:
Anisotropy
Binding
Cages
Chemical synthesis
Chemistry
Chemistry and Materials Science
Crystallization
Elastic deformation
Electron density
Inorganic Chemistry
Metal clusters
NMR
Nuclear magnetic resonance
Physical Chemistry
Ruthenium
Transition metals
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Summary:Tetranuclear cluster [Ru(μ 3 -CO)Cp] 4 (I) is synthesized as a minor product in the thermal reaction of cyclopentadiene with Ru 3 (CO) 12 aimed at preparing ruthenium dimer [Ru(CO) 2 Cp] 2 . The spectral ( 13 С and 1 H 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 Ru 4 (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(μ 3 -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.
ISSN:1070-3284
1608-3318
DOI:10.1134/S1070328423600249