Transformation of a μ 3 -Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ 3 -Sulfido Ligand

Hiroki Chikamori, Atsushi Tahara, Toshiro Takao

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2 Citations (Scopus)

Abstract

A triruthenium complex containing μ 32 (||)-benzyne and μ 3 -sulfido ligands, [(Cp∗Ru) 33 -S){μ 32 (||)-C 6 H 4 }(μ-H)] (2), was synthesized by the reaction of [(Cp∗Ru) 33 -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) 33 -S){μ 32 (||)-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) 33 -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 3 -benzyne 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) 33 -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) 33 -S){μ 322 (¥)-C 6 H 4 }(μ-H)] 2+ (8), was shown to be responsible for the uptake of water to yield μ-hydroxo complex 3.

Original languageEnglish
Pages (from-to)527-535
Number of pages9
JournalOrganometallics
Volume38
Issue number2
DOIs
Publication statusPublished - Jan 28 2019
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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