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: ジャーナルへの寄稿記事

2 引用 (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.

元の言語英語
ページ(範囲)527-535
ページ数9
ジャーナルOrganometallics
38
発行部数2
DOI
出版物ステータス出版済み - 1 28 2019
外部発表Yes

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Phenol
phenols
Ligands
ligands
Water
water
Deprotonation
Electrons
Benzene
Hydrogenation
hydrogenation
Amines
amines
electrons
Salts
benzene
Oxygen
salts
Oxidation
oxidation

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

これを引用

Transformation of a μ 3 -Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ 3 -Sulfido Ligand . / Chikamori, Hiroki; Tahara, Atsushi; Takao, Toshiro.

:: Organometallics, 巻 38, 番号 2, 28.01.2019, p. 527-535.

研究成果: ジャーナルへの寄稿記事

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title = "Transformation of a μ 3 -Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ 3 -Sulfido Ligand",
abstract = "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 3 -η 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 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) 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.",
author = "Hiroki Chikamori and Atsushi Tahara and Toshiro Takao",
year = "2019",
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T1 - Transformation of a μ 3 -Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ 3 -Sulfido Ligand

AU - Chikamori, Hiroki

AU - Tahara, Atsushi

AU - Takao, Toshiro

PY - 2019/1/28

Y1 - 2019/1/28

N2 - 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 3 -η 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 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) 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.

AB - 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 3 -η 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 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) 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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U2 - 10.1021/acs.organomet.8b00832

DO - 10.1021/acs.organomet.8b00832

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JO - Organometallics

JF - Organometallics

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