Nucleophilic Attack on an Electronically Unsaturated Triosmium Cluster Complex of 2-Methylbenzoxazole: An Unusual Oxidative Ring Opening

The reaction of the electron-deficient 6-methoxyquinolinate-substituted triosmium cluster [Os3(CO)9{μ3-η 1 ,κ 1-C9H5N(6-OMe)}(μ-H)] (1) with PPh3 proceeds readily at room temperature to afford the electron-precise adduct [Os3(CO)9(PPh3){μ-η 1 ,κ 1-C9H5N(6-OMe)}(μ-H)] (2), in which the PPh3 ligand is bound to the osmium that serves as the coordination site for the hydride and the metallated-carbon atom of the benzoheterocycle. This reaction also leads to a change in the hapticity of the 6-methoxyquinolinate ligand from μ3-η 1 ,κ 1 to μ-η 1 ,κ 1 as confirmed by X-ray crystallography. Thermolysis of 2 in boiling toluene furnishes five new triosmium clusters (3-7) as a result of ligand isomerization, decarbonylation and orthometallation of the ancillary PPh3 ligand. Clusters 3 and 4 are isomers of 2 and the location of the metal-bound hydride and PPh3 with respect to 6methoxyquinolinate moiety is the only difference between these isomers. Control experiments show that 5 is a decarbonylation product of 4 which converts in to 6 as a result of further decarbonylation with concomitant orthometallation of one of the phenyl rings of the coordinated PPh3 ligand, whilst 7 is formed from 6 through replacement of an equatorial 2 carbonyl of the nitrogen-bound osmium by PPh3 ligand. All the new clusters have been characterized by a combination of analytical and spectroscopic methods as well as by X-ray crystallography in the case of 2, 3, 6 and 7.

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Reaction of electron-deficient 6-methoxyquinolinate-substituted cluster [Os3(CO)9{μ3-η1,κ1-C9H5N(6-OMe)}(μ-H)] with PPh3: Thermally induced ligand isomerization, decarbonylation and orthometallation

Begum

Chowdhury

Ghosh

et al. 2018

Inorganica Chimica Acta

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Reactions of the face-capped benzothiazolate-substituted clusters Os3(CO)9(μ3,η2-C7H3NSR)(μ-H) (R = H, Me) with PPh3: Kinetic formation of Os3(CO)9(PPh3)(μ,η2-C7H3NSR)(μ-H) and thermally induced ligand isomerization

Begum

Chowdhury

Ghosh

et al. 2017

Journal of Organometallic Chemistry

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C‒H activation of caffeine at triruthenium and triosmium centers

Alam

Mia

Mamun

et al. 2021

Journal of Organometallic Chemistry

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Nucleophilic Attack on an Electronically Unsaturated Triosmium Cluster Complex of 2-Methylbenzoxazole: An Unusual Oxidative Ring Opening

Cited by 5 publications

References 28 publications

Reaction of electron-deficient 6-methoxyquinolinate-substituted cluster [Os3(CO)9{μ3-η1,κ1-C9H5N(6-OMe)}(μ-H)] with PPh3: Thermally induced ligand isomerization, decarbonylation and orthometallation

Reaction of electron-deficient 6-methoxyquinolinate-substituted cluster [Os3(CO)9{μ3-η1,κ1-C9H5N(6-OMe)}(μ-H)] with PPh3: Thermally induced ligand isomerization, decarbonylation and orthometallation

Reactions of the face-capped benzothiazolate-substituted clusters Os3(CO)9(μ3,η2-C7H3NSR)(μ-H) (R = H, Me) with PPh3: Kinetic formation of Os3(CO)9(PPh3)(μ,η2-C7H3NSR)(μ-H) and thermally induced ligand isomerization

C‒H activation of caffeine at triruthenium and triosmium centers

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