Reactions of the triosmium cluster Os3(μ-H)(μ-OH)(CO)10 with naphthols

Lum, Mien Wei; Leong, Weng Kee

doi:10.1016/j.jorganchem.2003.08.030

Cited by 11 publications

(3 citation statements)

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“…Trinuclear complexes containing a μ 3 -cyclohexadienonediyl ligand have been reported for Os 3 complexes; these were obtained from the reaction with phenols or naphthols . However, its formation via reductive C–O bond formation with μ 3 -benzyne ligand is unprecedented.…”

Section: Resultsmentioning

confidence: 92%

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Transformation of a μ₃-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ₃-Sulfido Ligand

2018

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A triruthenium complex containing μ 3 -η 2 (||)-benzyne and μ 3 -sulfido ligands, [(Cp*Ru) 3 (μ 3 -S){μ 3 -η 2 (||)-C 6 H 4 }(μ-H)] (2), was synthesized by the reaction of [(Cp*Ru) 3 (μ 3 -S)(μ-H) 3 ] (1) with benzene. Although 2 was stable toward oxygen and water, two-electron oxidation of 2 with a Ag(I) salt in the presence of water afforded the dicationic μ-hydroxo complex [(Cp*Ru) 3 (μ 3 -S){μ 3η 2 (||)-C 6 H 4 }(μ-OH)] 2+ (3). Treatment of 3 with amine resulted in the deprotonation of the μ-hydroxo ligand, and an unsaturated monocationic complex, [(Cp*Ru) 3 (μ 3 -S)(μ 3 -OC 6 H 4 -κO,κC)] + (4), which possesses a μ 3 -cyclohexadienonediyl ligand, was formed via reductive C−O bond formation between the μ 3benzyne and transient μ-oxo ligands. Phenol was extruded from the Ru 3 cluster upon the hydrogenation of 4 via the formation of a μ 3 -phenoxo complex, [(Cp*Ru) 3 (μ 3 -S){μ 3 -OPh}(μ-H)] + (5). The cyclic voltammogram of 2 shows two reversible one-electron redox waves, and a dicationic μ 3 -benzyne complex, [(Cp*Ru) 3 (μ 3 -S){μ 3 -η 2 :η 2 (⊥)-C 6 H 4 }(μ-H)] 2+ (8), was shown to be responsible for the uptake of water to yield μ-hydroxo complex 3.

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Section: Resultsmentioning

confidence: 92%

“…In contrast to 4 , the known triosmium complexes containing a μ 3 -cyclohexadienonediyl ligand were not fluxional . This is likely because of the cationic metal center of 4 , which reduces the back-donation to the μ 3 -OC 6 H 4 moiety.…”

Section: Resultsmentioning

confidence: 99%

Transformation of a μ₃-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ₃-Sulfido Ligand

2018

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“…The benzoheterocyclic clusters [Os 3 (CO) 9 (l 3 -benzoheterocycle)(l-H)] represent further examples of unsaturated 46-electron triosmium hydride complexes and over the past 10 years they have been shown to show to be reactive towards a wide range of substrates [10][11][12][13][14][15][16][17]. We have now investigated the reaction of one of these complexes, namely [Os 3 (CO) 9 (l 3 -C 7 H 4 NS)(l-H)] (1) [10], towards the activated alkyne dmad.…”

Section: Introductionmentioning

confidence: 99%

Cluster-mediated alkenyl isomerism and carbon–carbon bond formation: The reaction of the unsaturated benzothiazole cluster [Os3(CO)9(μ3-C7H4NS)(μ-H)] with dimethyl acetylenedicarboxylate

Uddin

Ghosh

Raha

et al. 2010

Journal of Organometallic Chemistry

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Isomerism in Molecular Metal Carbonyl Clusters

Cesari,

Femoni,

Forti

et al. 2024

Eur J Inorg Chem

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The present microreview focuses on different typologies of isomerism documented along the years for metal carbonyl clusters (MCCs), and outlines their analogies to other classes of ligand‐protected molecular clusters and nanoclusters. Isomerism in molecular MCCs is discussed within two main categories, that is, surface isomerism and core isomerism. The first Section presents some representative examples of surface isomerism involving inorganic (carbonyls and hydrides) and organic ligands, as well as isomerism due to ML fragments decorating the cluster surface. The second Section focuses on three major categories of core isomerism, that is: (1) isomers that mainly differ on M‐M distances; (2) isomers displaying different structures of the metal kernels; (3) isomers possessing almost identical metal kernels and ligand shells, but differing for the positions of different types of metal atoms within the metal kernel. The third Section briefly discusses two related and very rare cases of isomerism, that is, polymerisation and coordination isomerism. General conclusions are outlined in the final Section.

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Reactions of the triosmium cluster Os3(μ-H)(μ-OH)(CO)10 with naphthols

Cited by 11 publications

References 11 publications

Transformation of a μ₃-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ₃-Sulfido Ligand

Transformation of a μ₃-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ₃-Sulfido Ligand

Cluster-mediated alkenyl isomerism and carbon–carbon bond formation: The reaction of the unsaturated benzothiazole cluster [Os3(CO)9(μ3-C7H4NS)(μ-H)] with dimethyl acetylenedicarboxylate

Isomerism in Molecular Metal Carbonyl Clusters

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Reactions of the triosmium cluster Os3(μ-H)(μ-OH)(CO)10 with naphthols

Cited by 11 publications

References 11 publications

Transformation of a μ3-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ3-Sulfido Ligand

Transformation of a μ3-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ3-Sulfido Ligand

Cluster-mediated alkenyl isomerism and carbon–carbon bond formation: The reaction of the unsaturated benzothiazole cluster [Os3(CO)9(μ3-C7H4NS)(μ-H)] with dimethyl acetylenedicarboxylate

Isomerism in Molecular Metal Carbonyl Clusters

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Transformation of a μ₃-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ₃-Sulfido Ligand

Transformation of a μ₃-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ₃-Sulfido Ligand