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

研究成果: Article査読

2 被引用数 (Scopus)

抄録

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.

本文言語English
ページ(範囲)527-535
ページ数9
ジャーナルOrganometallics
38
2
DOI
出版ステータスPublished - 2019 1 28
外部発表はい

ASJC Scopus subject areas

  • 物理化学および理論化学
  • 有機化学
  • 無機化学

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