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
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Scientific Research in Innovative Areas “Molecular Activation Directed toward Straightforward Synthesis” from MEXT, Japan. H.C. also acknowledges the support from the Hiki Foundation, Tokyo Institute of Technology.
Publisher Copyright:
© 2018 American Chemical Society.
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
M3 - Article
AN - SCOPUS:85060633821
SN - 0276-7333
VL - 38
SP - 527
EP - 535
JO - Organometallics
JF - Organometallics
IS - 2
ER -