Trinuclear Clusters of Ruthenium and Osmium: (i) Introduction and Simple Neutral, Anionic and Hydrido Clusters

Deeming, Antony J.

doi:10.1016/b978-008046519-7.00067-8

Cited by 16 publications

(11 citation statements)

References 541 publications

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“…The geometry of the real compound 1 was also optimized assuming no symmetry element. The geometrical Table 1 Major DFT results computed for {Ru 3 Overall, there is a good agreement between the computed and the X-ray data.…”

Section: Dft Analysis Of the Electronic Structure Of Clustermentioning

confidence: 78%

“…On the other hand, there is no need to consider delocalization of the C C s bonding pairs in 4 to obtain the expected 50e − count for the open Ru 3 triangle, assuming that the m 2 -NS(O)MePh ligand, which exhibits a pyramidalized N atom [7], is a 3e − donor and the PhCCCCHPh ligand a 5e − donor. This is supported by EHT calculations in which no electron deficiency can be traced (HOMO -LUMO gap: 1.68 eV).…”

Section: Mo Analysis and Electron Counting In Clusters 2-5mentioning

confidence: 99%

“…Although a normal electron count of 48e − could not be ruled out for 1 (considering the m 3 -sulfoximido cap as a 5e − donor, which would imply an N − S + formalism), several arguments were in favor of the electrondeficiency of 1: capping N R ligands act as 4e − donors, and no 5e − -m 3 -N − R + cap has been reported so far [3]. The sulfur-nitrogen bond in 1 (1.566 A , ) [2] can be interpreted as an N S double bond in comparison with methionylsulfoximine (1.529 A , ) [4], which would leave 3e − on the nitrogen atom of the N S(O)MePh fragment, in accordance with an electron count of 46e − for the cluster.…”

Section: Introductionmentioning

confidence: 99%

“…We therefore introduced the chiral methylphenylsulfoximido ligand into the trinuclear ruthenium system by reaction of Ru 3 (CO) 12 with MePhS(O)NH. The only high-yield product of this reaction, Ru 3 (CO) 9 (m 2 -H)[m 3 -NS(O)MePh] (1, Eq. (1)), which we isolated in both enantiomeric forms and characterized by single-crystal X-ray crystallography, was considered to be an electron-deficient 46e − cluster (taking into account the sulfoximido cap as a 3e − ligand [2].…”

Section: Introductionmentioning

confidence: 99%

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Electron counting and bonding analysis in triruthenium clusters containing sulfoximido ligands: true or false electron-deficient systems?

Saillard¹

2001

Journal of Organometallic Chemistry

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Triruthenium clusters containing a methylphenylsulfoximido cap or bridge, Ru 3 (CO) 9 analyze the bonding present in the clusters and to establish the electron counting. They clearly show that a m 3 -sulfoximido group is not a 3e − ligand as one may be led to think at first sight, but rather acts as a three-orbital/5e − system, i.e. should be considered as isolobal to an N R − ligand. Because of some delocalization of its p-type orbitals on the sulfur and oxygen atoms, it is expected to bind slightly less strongly to metal atoms than classical imido ligands. Once in a m 2 coordination mode, the sulfoximido ligand retains a lone pair on its pyramidalized N atom and becomes a two-orbital/3e − ligand. It follows that clusters 1, 2, 4 and 5 are electron-precise, whereas cluster 3 is electron deficient with respect to the 18e − rule but obeys the polyhedral skeletal electron pair electron-counting rules. Consistently, all the calculated clusters exhibit large HOMO-LUMO gaps and no trace of electron deficiency can be found in their electronic structures.

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Section: Dft Analysis Of the Electronic Structure Of Clustermentioning

confidence: 78%

Section: Mo Analysis and Electron Counting In Clusters 2-5mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electron counting and bonding analysis in triruthenium clusters containing sulfoximido ligands: true or false electron-deficient systems?

Saillard¹

2001

Journal of Organometallic Chemistry

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“…The extensive ligand chemistry reported on the tri-osmium cluster [Os 3 (CO) 12 ] can be attributed to the robustness of the osmium compounds that are formed [1]. Several review articles demonstrate the versatility of osmium clusters to facilitate various organic transformations on the metal framework [2].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of the substituted products from the reaction of a bulky phosphite with [Os₃(CO)₁₂]

Meijboom

Muller

Mavunkal

2008

Journal of Coordination Chemistry

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Reaction of (acetonitrile)-undeca(carbonyl)-tri-osmium and tris(2,4-di-tert-butylphenyl) phosphite yielded the phosphite clusters [Os 3 (CO) 11 L] (4) and [Os 3 (CO) 10 L 2 ] (5). These compounds were characterized spectroscopically and the molecular structure of 5 was determined by single crystal X-ray diffraction, the first reported structural analysis of a tri-osmium cluster containing aromatic phosphite ligands. Compound 5 crystallized in the triclinic space group P " 1, and revealed an equatorial trans-trans position of the bulky phosphite ligands.

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Polynuclear Organometallic Cluster Complexes

Keister

2005

Encyclopedia of Inorganic Chemistry

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The title refers to molecular compounds containing three or more transition metal atoms and hydrocarbyl ligands as a part of the metal–carbon cluster core. Because the chemistry of trimetallic clusters is the most well developed, these examples are to be stressed. Selected examples are presented to illustrate the principles of structure and bonding of organometallic clusters, synthetic approaches, and chemical reactions, including ligand substitution, oxidative addition, intramolecular insertion, protonation of metal–metal bonds and coordinated ligands, nucleophilic attack on coordinated ligands, and ligand fluxionality. The chemistry of these clusters is exemplified by trimetallic clusters containing hydrocarbon fragments of one, two, or three carbon atoms. While, many of the features of cluster chemistry are common with those of organometallic complexes containing a single metal atom, there are notable differences in structures and reactivities owing to the tendencies of ligands to bridge between two or more metal atoms and for ligands bound to only a single metal atom to undergo facile intramolecular migrations between metal atoms. These distinctions give rise to the ‘metal‐cluster‐metal surface analogy’ in which structural and spectroscopic features of organometallic clusters are used as models for hydrocarbons chemisorbed on metal surfaces.

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Trinuclear Clusters of Ruthenium and Osmium: (i) Introduction and Simple Neutral, Anionic and Hydrido Clusters

Cited by 16 publications

References 541 publications

Electron counting and bonding analysis in triruthenium clusters containing sulfoximido ligands: true or false electron-deficient systems?

Electron counting and bonding analysis in triruthenium clusters containing sulfoximido ligands: true or false electron-deficient systems?

Synthesis and characterization of the substituted products from the reaction of a bulky phosphite with [Os₃(CO)₁₂]

Polynuclear Organometallic Cluster Complexes

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Trinuclear Clusters of Ruthenium and Osmium: (i) Introduction and Simple Neutral, Anionic and Hydrido Clusters

Cited by 16 publications

References 541 publications

Electron counting and bonding analysis in triruthenium clusters containing sulfoximido ligands: true or false electron-deficient systems?

Electron counting and bonding analysis in triruthenium clusters containing sulfoximido ligands: true or false electron-deficient systems?

Synthesis and characterization of the substituted products from the reaction of a bulky phosphite with [Os3(CO)12]

Polynuclear Organometallic Cluster Complexes

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Product

Resources

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Synthesis and characterization of the substituted products from the reaction of a bulky phosphite with [Os₃(CO)₁₂]