A Redetermination of the Crystal Structure of Bis(cyclopentadienyldicarbonylruthenium)

Mague, Joel T.

doi:10.1107/s0108270194005445

Cited by 18 publications

(15 citation statements)

References 4 publications

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“…In summary, the molecules examined in this study are structurally similar to recently popular organometallic complexes. Since all the molecules except Ru 2 have been well characterized by X-ray crystallography, the calculated bond lengths can be readily compared with those of experimental values. − For Ru 2 , the result of recent high-level ab initio calculations (the second-order multiconfigurational perturbation theory, CASPT2) has been considered as a reference value . The optimized geometrical parameters of the molecular structures are summarized in Tables S2–S7 in the Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

Performance of Density Functional Theory and Relativistic Effective Core Potential for Ru-Based Organometallic Complexes

et al. 2016

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Herein a performance assessment of density functionals used for calculating the structural and energetic parameters of bi- and trimetallic Ru-containing organometallic complexes has been performed. The performance of four popular relativistic effective core potentials (RECPs) has also been assessed. On the basis of the calculated results, the MN12-SX (range-separated hybrid functional) demonstrates good performance for calculating the molecular structures, while MN12-L (local functional) performs well for calculating the energetics, including that of the Ru-Ru bond breaking process. The choice of appropriate density functional is a crucial factor for calculating the energetics. The LANL08 demonstrates the lowest performance of the RECPs for calculating the molecular structures, especially the Ru-Ru bond length.

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Section: Resultsmentioning

confidence: 99%

Performance of Density Functional Theory and Relativistic Effective Core Potential for Ru-Based Organometallic Complexes

et al. 2016

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“…Reaction between [CpRu(CO) 2 ] 2 and C 60 : Geometry and Energy Changes. In all four tautomers of [CpRu-(CO) 2 ] 2 , 41−43 the trans-B isomer containing two bridging carbonyls was experimentally found in crystal; 44 In the second step, the η 2 -coordinated Ru 1 −C bond changes into an η 1 -coordinated bond concomitantly with the breaking of the Ru 1 −(CO)−Ru 2 bridge. The Ru 2 center moves around the two six-member rings in either anticlockwise or clockwise manner in TS2a or TS2b, respectively (Scheme 2).…”

Section: Inorganic Chemistrymentioning

confidence: 99%

[2 + 2]-type Reaction of Metal–Metal σ-Bond with Fullerene Forming an η¹-C₆₀ Metal Complex: Mechanistic Details of Formation Reaction and Prediction of a New η¹-C₆₀ Metal Complex

2017

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C[CpRu(CO)] is only one transition-metal fullerene complex with pure η-coordinated bonds, which was recently synthesized through the reaction between dinuclear Ru complex [CpRu(CO)] and C. Though new properties can be expected in the η-coordinated metal-fullerene complex, its characteristic features are unclear, and the [2 + 2]-type formation reaction is very slow with a very small yield. A density functional theory study discloses that the η-coordinated bond is formed by a large overlap between the Ru d orbital and C p one involved in the lowest unoccupied molecular orbital (LUMO) (π*) of C unlike the well-known η-coordinated metal-fullerene complex which has a π-type coordinate bond with metal d orbital. The binding energy per one Ru-C bond is much smaller than those of η-coordinated Pt(PMe)(C) and IrH(CO)(PH)(C) because the Ru d orbital exists at low energy. The formation reaction occurs via Ru-Ru bond cleavage on the C surface followed by a direction change of CpRu(CO) to afford C[CpRu(CO)] in a stepwise manner via two asymmetrical transition states to avoid a symmetry-forbidden character. The calculated Gibbs activation energy (ΔG°) is very large and the Gibbs reaction energy (ΔG°) is moderately negative, which are consistent with a very slow reaction rate and very small yield. The charge transfer from CpRu(CO) to fullerene CT(Ru → C) is important in the reaction, but it is small due to the presence of the Ru d orbital at low energy, which is the reason for the large ΔG° and moderately negative ΔG°. The use of Li@C is theoretically predicted to accelerate the reaction and increase the yield of Li@C[CpRu(CO)], because the CT(Ru → C) is enhanced by the low energy LUMO of Li@C. It is also predicted that Li@C[Re(CO)(PMe)] is a next promising target for the synthesis of the η-coordinated metal-fullerene complex, but syntheses of C[Co(CO)], C[Re(CO)], Li@C[Co(CO)], and Li@C[Re(CO)] are difficult. The use of nonpolar solvent is another important factor for the synthesis of the η-coordinated metal complex with Li@C.

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“…(CH 2 CH 2 )HÁ Á ÁO-C = 2.7 A . Similar contacts appear to dominate in other substituted Cp * counterparts [2] as well as in Cp 2 Ru 2 (CO) 4 [11,12], the shortest intermolecular contacts thus involving hydrogen atoms of the cyclopentadienyl ring or of substituents on these rings and oxygen atoms of either terminal or bridging carbonyl groups. These contacts are of the order of 2.6-2.7 A [2,11] with 2.52 A observed in a low temperature study of Cp 2 Ru 2 (CO) 4 [12].…”

Section: Preparation Of (C 5 Me 4 Hex) 2 Ru 2 (Co)mentioning

confidence: 82%

Synthesis, structure and some reactions of (C5Me4hex)2Ru2(CO)4

Ngubane

Håkansson

Jagner

et al. 2008

Journal of Organometallic Chemistry

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A Redetermination of the Crystal Structure of Bis(cyclopentadienyldicarbonylruthenium)

Cited by 18 publications

References 4 publications

Performance of Density Functional Theory and Relativistic Effective Core Potential for Ru-Based Organometallic Complexes

Performance of Density Functional Theory and Relativistic Effective Core Potential for Ru-Based Organometallic Complexes

[2 + 2]-type Reaction of Metal–Metal σ-Bond with Fullerene Forming an η¹-C₆₀ Metal Complex: Mechanistic Details of Formation Reaction and Prediction of a New η¹-C₆₀ Metal Complex

Synthesis, structure and some reactions of (C5Me4hex)2Ru2(CO)4

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A Redetermination of the Crystal Structure of Bis(cyclopentadienyldicarbonylruthenium)

Cited by 18 publications

References 4 publications

Performance of Density Functional Theory and Relativistic Effective Core Potential for Ru-Based Organometallic Complexes

Performance of Density Functional Theory and Relativistic Effective Core Potential for Ru-Based Organometallic Complexes

[2 + 2]-type Reaction of Metal–Metal σ-Bond with Fullerene Forming an η1-C60 Metal Complex: Mechanistic Details of Formation Reaction and Prediction of a New η1-C60 Metal Complex

Synthesis, structure and some reactions of (C5Me4hex)2Ru2(CO)4

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[2 + 2]-type Reaction of Metal–Metal σ-Bond with Fullerene Forming an η¹-C₆₀ Metal Complex: Mechanistic Details of Formation Reaction and Prediction of a New η¹-C₆₀ Metal Complex