The structure of di-μ-chloro-bis[chloro(η6-hexamethylbenzene)ruthenium(II)]–chloroform (1/2)

McCormick, Fred B.; Gleason, William B.

doi:10.1107/s0108270187011909

Cited by 16 publications

(6 citation statements)

References 6 publications

(7 reference statements)

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“…The geometry regarding the ruthenium ion moiety consists of a distorted tetrahedron, with the cyclophane and the other ligands adopting a piano-stool configuration. The distance from the ruthenium ion to the centroid of the coordinated ring is on average 1.7 Å, in good agreement with many reported distances, which range from 1.64 to 1.79 Å. − The results presented show that the coordination and the presence of different substituents on ring B affects the charge distribution and consequently the tension on the cyclophane structure, while the Ru–A distances (the distance between the Ru atom and the centroid of ring A) are not affected considerably, with values ranging around 1.7 Å.…”

Section: Resultssupporting

confidence: 88%

Ruthenophanes: Evaluating Cation−π Interactions in [Ru(η⁶-C₁₆H₁₂R₄)(NH₃)₃]^2+/3+ Complexes. A Computational Insight

et al. 2014

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The nature of cation−π interactions in a set of [Ru(η6-C16H12R4)(NH3)3]2+3+ (R = F, CN, CH3, and others), complexes was investigated with Su–Li energy decomposition analysis and the natural orbitals for chemical valence and the extended transition state method EDA-NOCV. The long-distance effects of electron-donating and electron-withdrawing substituents as well as protonation of the ipso carbon on the nature of cation−π interactions were investigated. Both energy decomposition analyses, Su–Li EDA and EDA-NOCV, are in total agreement, showing that the presence of electron-donating substituents such as CH3, NH2, and H3CO tends to stabilize the ruthenium–arene interaction while electron-withdrawing substituents such as F, CN, and NO2 tend to weaken such interactions. The electrostatic component of the ruthenium–arene interaction is the most affected by the substitution, despite the fact that the covalent character is much more significant than the electrostatic character. EDA-NOCV reveals that the most important orbital stabilization comes from donation and back-donation between the interacting fragments, while the σ density deformations present a moderate contribution to total orbital stabilization energy in ruthenium–arene interactions of complexes 1–8.

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Section: Resultssupporting

confidence: 88%

Ruthenophanes: Evaluating Cation−π Interactions in [Ru(η⁶-C₁₆H₁₂R₄)(NH₃)₃]^2+/3+ Complexes. A Computational Insight

et al. 2014

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“…21 The separation between two ruthenium ions was 3.648(2) Å, and that between two chlorides was 3.286(2) Å, indicating no direct Ru‚‚‚Ru and Cl‚‚‚Cl interactions. The geometry of the Ru 2 Cl 2 core was similar to those of reported structures such as 23 and [Ru 2 Cl 2 (η 6 -hexamethylbenzene) 2 ], 24 which were determined in the space group of P1 h with the center of symmetry at similar positions. The pyridine rings of the TPA ligand were divided into two types: two pyridine moieties were trans to each other, namely equatorial, and one is trans to the µ-Clligand, namely axial.…”

Section: Synthesissupporting

confidence: 77%

Synthesis and Characterization of Mononuclear and Dinuclear Ruthenium Complexes with Tris(2-pyridylmethyl)amine and Tris(5-methyl-2-pyridylmethyl)amine

et al. 1998

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Novel Ru(II) and Ru(III) complexes having TPA (tris(2-pyridylmethyl)amine, L1) and 5-Me(3)-TPA (tris(5-methyl-2-pyridylmethyl)amine, L2) were prepared to establish their synthetic routes and to elucidate coordination geometry and interactions between tightly bound tripodal tetradentate ligands and Ru(II)/Ru(III) centers. They include mononuclear Ru(II) complexes [RuCl(DMSO)(L)]ClO(4) (1 (L1), 2 (L2)), dinuclear bis-&mgr;-chloro Ru(II) complexes [RuCl(L)](2)(ClO(4))(2) (3 (L1), 4 (L2)), and mononuclear Ru(III) complexes [RuCl(2)(L)]ClO(4) (5 (L1), 6 (L2)). They were characterized by X-ray crystallography (for 2, 3, and 5), (1)H NMR spectroscopy, and cyclic voltammetry. For compound 2, the crystal structure was determined to possess S-bound DMSO ligand which was trans to pyridine and Cl(-) trans to the tertiary amino group of L2, and this isomer was obtained exclusively. Complex 1 was also isolated as a single isomer. Complex 3 was revealed to be a dinuclear bis-&mgr;-chloro Ru(II) species with the center of symmetry midway between two Cl(-). (1)H NMR spectra of Ru(II) complexes 1-4, the molecular structure of 2, and comparison of the molecular structure of 3 with 5 suggest that the interaction between the Ru(II) center, pyridyl moieties, and the DMSO ligand is strengthened by pi-back-bonding from the Ru(II) center to the ligands in addition to sigma-bonding of the tertiary amino group. Electrochemical measurements on 1-6 in CH(3)CN revealed that the methyl groups on pyridyl rings exert electron-donating effects onto the Ru centers to lower each redox process and such effect strengthens the Ru-S bonding in 2 compared with that in 1, accommodating pi-back-bonding from Ru(II) center to other pi-acceptors such as DMSO in 2 enough to prevent isomerization of DMSO binding mode. The dinuclear complexes 3 and 4 showed relatively large comproportionation constants, which suggest mixed-valent Ru(II)Ru(III) states would be stabilized.

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“…It consists of each Ru(II) atom bonded to a hexamethylbenzene ligand, two nitrogen atoms of azide groups and one chlorine atom, maintaining centrosymmetry. The Ru-Cl bond distances are 2.394(5) and 2.421(5) Å , which are close (3) to those in the starting dimeric complex 1 [23]. The Ru-N bond lengths involving the bridging nitrogen moieties Ru(A)-N(1), Ru(A)-N(4), Ru(B)-N(1) and Ru(B)-N(4) are 2.120 (14), 2.138(13), 2.151(12) and 2.168(14) Å , respectively, very similar to those found in the complex 2.…”

Section: Molecular Structuresmentioning

confidence: 77%

Syntheses and characterization of [(η6-C6Me6)Ru(μ-N3)(X)]2 (X=N3 and Cl) complexes and their reactions towards mono- and bidentate ligands

Govindaswamy¹,

Carroll²,

Mozharivskyj³

et al. 2005

Journal of Organometallic Chemistry

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The structure of di-μ-chloro-bis[chloro(η6-hexamethylbenzene)ruthenium(II)]–chloroform (1/2)

Abstract: Abstract. [Ru2C12(C 12Hls)2].2CHCI3, M r = 907.26, triclinic, Pi, a=10.192(1), b=10.953(1), c--

Cited by 16 publications

References 6 publications

Ruthenophanes: Evaluating Cation−π Interactions in [Ru(η⁶-C₁₆H₁₂R₄)(NH₃)₃]^2+/3+ Complexes. A Computational Insight

Ruthenophanes: Evaluating Cation−π Interactions in [Ru(η⁶-C₁₆H₁₂R₄)(NH₃)₃]^2+/3+ Complexes. A Computational Insight

Synthesis and Characterization of Mononuclear and Dinuclear Ruthenium Complexes with Tris(2-pyridylmethyl)amine and Tris(5-methyl-2-pyridylmethyl)amine

Syntheses and characterization of [(η6-C6Me6)Ru(μ-N3)(X)]2 (X=N3 and Cl) complexes and their reactions towards mono- and bidentate ligands

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The structure of di-μ-chloro-bis[chloro(η6-hexamethylbenzene)ruthenium(II)]–chloroform (1/2)

Abstract: Abstract. [Ru2C12(C 12Hls)2].2CHCI3, M r = 907.26, triclinic, Pi, a=10.192(1), b=10.953(1), c--

Cited by 16 publications

References 6 publications

Ruthenophanes: Evaluating Cation−π Interactions in [Ru(η6-C16H12R4)(NH3)3]2+/3+ Complexes. A Computational Insight

Ruthenophanes: Evaluating Cation−π Interactions in [Ru(η6-C16H12R4)(NH3)3]2+/3+ Complexes. A Computational Insight

Synthesis and Characterization of Mononuclear and Dinuclear Ruthenium Complexes with Tris(2-pyridylmethyl)amine and Tris(5-methyl-2-pyridylmethyl)amine

Syntheses and characterization of [(η6-C6Me6)Ru(μ-N3)(X)]2 (X=N3 and Cl) complexes and their reactions towards mono- and bidentate ligands

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Ruthenophanes: Evaluating Cation−π Interactions in [Ru(η⁶-C₁₆H₁₂R₄)(NH₃)₃]^2+/3+ Complexes. A Computational Insight

Ruthenophanes: Evaluating Cation−π Interactions in [Ru(η⁶-C₁₆H₁₂R₄)(NH₃)₃]^2+/3+ Complexes. A Computational Insight