Dinuclear and Polynuclear Ruthenium Non-cluster Compounds

The complex {(η 5 -C 5 H 3 ) 2 (SiMe 2 ) 2 }Ru 2 (CO) 4 (1), which features the doubly linked dicyclopentadienyl ligand (η 5 -C 5 H 3 ) 2 (SiMe 2 ) 2 , reacts with phosphines (PMe 3 , PCy 3 , PPh 3 ) to give {(η 5 -C 5 H 3 ) 2 (SiMe 2 ) 2 }Ru 2 (CO)(µ-CO) 2 (PR 3 ) (2a-c), with halogens X 2 (X ) Cl, Br, I) to give the Ru-Ru-cleaved products {(η 5 -C 5 H 3 ) 2 (SiMe 2 ) 2 }Ru 2 (CO) 4 (X) 2 (3a-c), with X 2 and AgTfO to give [{(η 5 -C 5 H 3 ) 2 (SiMe 2 ) 2 }Ru 2 (CO) 4 (µ-X)] + TfO -(X ) Cl, Br, I; 4a-c), and with SnCl 2 to give {(η 5 -C 5 H 3 ) 2 (SiMe 2 ) 2 }Ru 2 (CO) 4 (µ-SnCl 2 ) (5), resulting from the insertion of SnCl 2 into the Ru-Ru bond. Reduction of 1 with Na/Hg generates [{(η 5 -C 5 H 3 ) 2 (SiMe 2 ) 2 }Ru 2 (CO) 4 ] 2-(6), which reacts with (η 5 -C 5 H 5 ) 2 TiCl 2 to give {(η 5 -C 5 H 3 ) 2 (SiMe 2 ) 2 }Ru 2 (CO) 4 {µ-Ti(η 5 -C 5 H 5 ) 2 } (7). Ultraviolet photolysis of 1 with diphenylacetylene and phenylacetylene yields a series of five dinuclear Ru complexes (8-10, 12, 13) containing one or two bridging acetylene units. The rigidity of the doubly linked (η 5 -C 5 H 3 ) 2 (SiMe 2 ) 2 ligand substantially influences the reactivity and structures of the complexes. Molecular structures of 1, 2a, 3c, 5, 9, 10, and 12 as determined by X-ray diffraction studies are also presented.

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Reactions of the Dinuclear Ruthenium Complex {(η⁵-C₅H₃)₂(SiMe₂)₂}Ru₂(CO)₄, Featuring a Doubly Linked Dicyclopentadienyl Ligand

Ovchinnikov

Klein

Guzei

et al. 2002

Organometallics

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

Osintseva,

Semeikin,

Dolgushin

et al. 2023

Russ J Coord Chem

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SYNTHESIS AND FEATURES OF THE MOLECULAR AND CRYSTAL STRUCTURE OF THE Cp4Ru4(µ3-CO)4 CLUSTER

Osintseva,

Semeikin,

Dolgushin

et al. 2023

Koordinacionnaâ himiâ

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When preparing the ruthenium dimer [Ru(CO)2Cp]2 in the thermal reaction of cyclopentadiene with Ru3(CO)12, the tetranuclear cluster [Ru(μ3-CO)Cp]4 (I) was obtained as a minor product. Spectral (13C and 1H NMR, IR) and structural studies were carried out for cluster I. By crystallization under different conditions, two types of dark cherry crystals were obtained, cluster I itself (crystal 1) and its tetrahydrate (crystal 2), the structure of which was determined by X-ray diffraction. Structural data for 1 and 2 have been deposited in the Cambridge Structural Data Center (CCDC nos. 2241197 and 2241199, respectively; deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk). Based on a comparative analysis of cluster geometry, it is shown that the distortion of the Ru4(CO)4 framework in I from ideal Td symmetry in the structure of a pure compound is determined by the anisotropy of intermolecular contacts in the crystal. Features of chemical bonding in the [Ru(μ3-CO)Cp]4 cluster and its iron-containing analogue were studied using DFT calculations using topological analysis of electron density to compare energy characteristics and effective force constant bonding interactions. The necessity of using criteria for elastic deformations of interatomic interactions (force constants) for the correct description of structural and chemical phenomena, for example, such as the structural non-rigidity of the framework of transition metal clusters, has been demonstrated.

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Dinuclear and Polynuclear Ruthenium Non-cluster Compounds

Cited by 3 publications

References 94 publications

Reactions of the Dinuclear Ruthenium Complex {(η⁵-C₅H₃)₂(SiMe₂)₂}Ru₂(CO)₄, Featuring a Doubly Linked Dicyclopentadienyl Ligand

Reactions of the Dinuclear Ruthenium Complex {(η⁵-C₅H₃)₂(SiMe₂)₂}Ru₂(CO)₄, Featuring a Doubly Linked Dicyclopentadienyl Ligand

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

SYNTHESIS AND FEATURES OF THE MOLECULAR AND CRYSTAL STRUCTURE OF THE Cp4Ru4(µ3-CO)4 CLUSTER

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Dinuclear and Polynuclear Ruthenium Non-cluster Compounds

Cited by 3 publications

References 94 publications

Reactions of the Dinuclear Ruthenium Complex {(η5-C5H3)2(SiMe2)2}Ru2(CO)4, Featuring a Doubly Linked Dicyclopentadienyl Ligand

Reactions of the Dinuclear Ruthenium Complex {(η5-C5H3)2(SiMe2)2}Ru2(CO)4, Featuring a Doubly Linked Dicyclopentadienyl Ligand

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

SYNTHESIS AND FEATURES OF THE MOLECULAR AND CRYSTAL STRUCTURE OF THE Cp4Ru4(µ3-CO)4 CLUSTER

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Reactions of the Dinuclear Ruthenium Complex {(η⁵-C₅H₃)₂(SiMe₂)₂}Ru₂(CO)₄, Featuring a Doubly Linked Dicyclopentadienyl Ligand

Reactions of the Dinuclear Ruthenium Complex {(η⁵-C₅H₃)₂(SiMe₂)₂}Ru₂(CO)₄, Featuring a Doubly Linked Dicyclopentadienyl Ligand