Photolysis of triruthenium μ3-alkyne complexes capped by a μ3-oxo ligand

Kaneko, Takeshi; Murotani, Eisuke; Tenjimbayashi, Ryu-ichi; Suzuki, Hiroharu; Takao, Toshiro

doi:10.1016/j.jorganchem.2015.10.016

Cited by 4 publications

(7 citation statements)

References 55 publications

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“…Similar to the μ 3 -acetylido complexes supported by a μ 3 -oxo ligand, the μ 3 -ethynyl ligand in 6 rotated on the Ru 3 plane at increased temperatures. Although the 1 H NMR spectrum recorded at 25 °C displayed two sharp Cp* signals with an intensity ratio of 2:1, they became broad and coalesced with increasing temperature, as shown in Figure S13 in the Supporting Information.…”

supporting

confidence: 77%

“…This chemical shift is comparable to the methine signal of the analogous μ 3 -oxo complex, [(Cp*Ru) 3 (μ-H)(μ 3 -O)(μ 3 -η 2 -HCCPh)] (δ 8.50 ppm). 21 The 1 H NMR spectrum of 8 also displayed a singlet corresponding to the hydride at δ −25.47 ppm.…”

mentioning

confidence: 99%

“…Because of its low population, 8 could not be fully characterized; however, the formation of a μ 3 -alkyne ligand was strongly inferred by the 1 H NMR signal resonating at δ 8.20 ppm, which was assigned to the methine proton at the alkyne ligand. This chemical shift is comparable to the methine signal of the analogous μ 3 -oxo complex, [(Cp*Ru) 3 (μ-H)(μ 3 -O)(μ 3 -η 2 -HCCPh)] (δ 8.50 ppm) . The 1 H NMR spectrum of 8 also displayed a singlet corresponding to the hydride at δ −25.47 ppm.…”

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confidence: 99%

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Formation of a μ₃-Acetylide on a Ru₃ Cluster via Coupling of μ-Methylene with Isocyanide Accompanied by Elimination of Amine: A Model of Hydrogen-Assisted C–C Bond Formation on a Metal Surface

Chikamori

Takao

2019

Organometallics

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A μ3-methylidyne complex of ruthenium, [(Cp*Ru)3(μ3-CH)(μ-H)2(μ3-S)] (3; Cp* = (C5Me5)Ru), was synthesized by the reaction of [{Cp*Ru(μ-H)}3(μ3-H)2] (1) with thioanisole. Complex 3 isomerized to a μ-methylene intermediate via reductive C–H bond formation, which could uptake a two-electron donor, E, to yield [(Cp*Ru)3(μ-CH2)(μ-H)(μ3-S)(μ-E)] (4, E = CO; 5, E = t-BuNC). Although the μ-carbonyl complex 4 did not undergo C–C bond formation, thermolysis of 5 resulted in formation of the μ3-ethynyl complex [(Cp*Ru)3(μ3-CCH)(μ3-S)] (6), along with elimination of t-BuNH2. In the presence of CF3CH2OH, C–C bond formation proceeded at 25 °C and afforded μ3-aminovinylidene complex [(Cp*Ru){μ3-η2-C = C(N t BuH)H}(μ-H)(μ3-S)] (7), which was also transformed to 6 upon heating at 80 °C. Although C–C bond formation does not occur in the CO analogue, formation of 6 via the reaction with t-BuNC can be viewed as a model of H-assisted C–C bond formation for Fischer–Tropsch synthesis.

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confidence: 77%

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confidence: 99%

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confidence: 99%

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Formation of a μ₃-Acetylide on a Ru₃ Cluster via Coupling of μ-Methylene with Isocyanide Accompanied by Elimination of Amine: A Model of Hydrogen-Assisted C–C Bond Formation on a Metal Surface

Chikamori

Takao

2019

Organometallics

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“…These spectra indicate the pseudo- C s symmetry of 2 ; thus, the hydrido ligand should be located at the Ru–Ru edge to which the benzyne ligand is σ-bonded. The hydrido ligand resonated at δ −26.38 ppm, and the chemical shift is similar to that of the hydrido ligand in the μ 3 -oxo−μ 3 -η 2 -alkyne complex …”

Section: Resultsmentioning

confidence: 96%

“…The hydrido ligand resonated at δ −26.38 ppm, and the chemical shift is similar to that of the hydrido ligand in the μ 3 -oxo−μ 3 -η 2 -alkyne complex. 9 A single crystal suitable for X-ray diffraction (XRD) studies was obtained using the Et Cp analogue of 2, [( Et CpRu) 3 (μ 3 -S){μ 3 -η 2 (||)-C 6 H 4 }(μ-H)] (2′) ( Et Cp = η 5 -C 5 EtMe 4 ), and the structure of 2′ is shown in Figure 1. Because the benzyne ligand is disordered over two positions, it is difficult to discuss bond lengths and angles precisely.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Transformation of a μ₃-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ₃-Sulfido Ligand

2018

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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 3η 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 3benzyne 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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Photo-Induced Reaction of CpRu(μ-H)₄RuCp with Arenes Resulting in Irreversible Formation of μ-η²:η²-Cyclohexadiene Complexes

et al. 2022

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In contrast to the thermal reaction of [Cp*Ru(μ-H)4RuCp*] (1: Cp* = η5-C5Me5) with benzene at 70 °C yielding an equilibrium mixture of 1 and [{Cp*Ru(μ-H)}2(μ-η2:η2-C6H8)] (2), the UV irradiation of 1 at 25 °C in benzene at 365 nm exclusively produced the dinuclear cyclohexadiene complex 2. The photo-induced reaction of 1 featured remarkably high tolerance toward substituted benzene, including toluene and p-xylene. The photo-induced reaction of 1 with toluene afforded a regio-isomeric mixture of bridging methylcyclohexadiene complexes 5a and 5b in high yields, although the thermal reaction of 1 with toluene did not proceed. Dearomatization via insertion into the Ru–H bond did not occur in the reaction with the fused aromatic system due to the preservation of the additional aromatic system. The η2:η2-5,6-benzocyclohexadiene complex, [{Cp*Ru(μ-H)}2(μ-η2:η2-C10H8)] (7), was selectively obtained in the photo-induced reaction of 1 with naphthalene. Photochemically induced transient species with an expanded Ru2 skeleton were proposed based on the thermal reaction of 2,6-dimethylcyclohexa-1,3-diene complex, [{Cp*Ru(μ-H)}2(μ-η2:η2-Me2C6H6)] (6), with toluene, yielding the mixture of 5a and 5b. Time-dependent density functional theory calculations of 1 provided insight into the mechanism.

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Photolysis of triruthenium μ3-alkyne complexes capped by a μ3-oxo ligand

Cited by 4 publications

References 55 publications

Formation of a μ₃-Acetylide on a Ru₃ Cluster via Coupling of μ-Methylene with Isocyanide Accompanied by Elimination of Amine: A Model of Hydrogen-Assisted C–C Bond Formation on a Metal Surface

Formation of a μ₃-Acetylide on a Ru₃ Cluster via Coupling of μ-Methylene with Isocyanide Accompanied by Elimination of Amine: A Model of Hydrogen-Assisted C–C Bond Formation on a Metal Surface

Transformation of a μ₃-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ₃-Sulfido Ligand

Photo-Induced Reaction of CpRu(μ-H)₄RuCp with Arenes Resulting in Irreversible Formation of μ-η²:η²-Cyclohexadiene Complexes

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Photolysis of triruthenium μ3-alkyne complexes capped by a μ3-oxo ligand

Cited by 4 publications

References 55 publications

Formation of a μ3-Acetylide on a Ru3 Cluster via Coupling of μ-Methylene with Isocyanide Accompanied by Elimination of Amine: A Model of Hydrogen-Assisted C–C Bond Formation on a Metal Surface

Formation of a μ3-Acetylide on a Ru3 Cluster via Coupling of μ-Methylene with Isocyanide Accompanied by Elimination of Amine: A Model of Hydrogen-Assisted C–C Bond Formation on a Metal Surface

Transformation of a μ3-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ3-Sulfido Ligand

Photo-Induced Reaction of Cp*Ru(μ-H)4RuCp* with Arenes Resulting in Irreversible Formation of μ-η2:η2-Cyclohexadiene Complexes

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Formation of a μ₃-Acetylide on a Ru₃ Cluster via Coupling of μ-Methylene with Isocyanide Accompanied by Elimination of Amine: A Model of Hydrogen-Assisted C–C Bond Formation on a Metal Surface

Formation of a μ₃-Acetylide on a Ru₃ Cluster via Coupling of μ-Methylene with Isocyanide Accompanied by Elimination of Amine: A Model of Hydrogen-Assisted C–C Bond Formation on a Metal Surface

Transformation of a μ₃-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ₃-Sulfido Ligand

Photo-Induced Reaction of CpRu(μ-H)₄RuCp with Arenes Resulting in Irreversible Formation of μ-η²:η²-Cyclohexadiene Complexes