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 10 publications

(3 citation statements)

References 11 publications

(14 reference 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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Functions Containing Two Atoms of the Same Metallic Element

Sadimenko

2005

Comprehensive Organic Functional Group Transformations II

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

Cited by 10 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

Functions Containing Two Atoms of the Same Metallic Element

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

Cited by 10 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

Functions Containing Two Atoms of the Same Metallic Element

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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