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

Research output: Contribution to journalArticle

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

Fingerprint

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

Cite this

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.

In: Organometallics, Vol. 38, No. 2, 28.01.2019, p. 527-535.

Research output: Contribution to journalArticle

@article{fc7a51096cbb403b947f015b1bd8fa67,
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",
month = "1",
day = "28",
doi = "10.1021/acs.organomet.8b00832",
language = "English",
volume = "38",
pages = "527--535",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

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.

UR - http://www.scopus.com/inward/record.url?scp=85060633821&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85060633821&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.8b00832

DO - 10.1021/acs.organomet.8b00832

M3 - Article

AN - SCOPUS:85060633821

VL - 38

SP - 527

EP - 535

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 2

ER -