Synthesis of butadiene via vinyl–ethylene combination at a diruthenium centre

Bruce, Gregg C.; Knox, Selby A. R.; Phillips, Andrew J.

doi:10.1039/c39900000716

Cited by 19 publications

(15 citation statements)

References 8 publications

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“…[Ru 2 (η 5 -C 5 H 5 ) 2 (CO) 2 -Also with propene (B), 1-butene (C), or (E)-2-butene (D) (CH 3 CN)(µ-vinyl)] ϩ reacts with ethylene to [Ru 2 (η 5 -C 5 H 5 ) 2hydrido-dienyl, 2-alkene-1,1-diyl and 1,3-diene complexes (CO) 2 (µ-H)(µ-η 2:2 -1,3-butadiene)] ϩ and by deprotonation are formed. With B and C in addition the thermolabile, to [Ru 2 (η 5 -C 5 H 5 ) 2 (CO) 2 (µ-η 2:2 -1,3-butadiene)] [34] . Simisimple substitution products (µ-η 2:2 -acetylene)tricarbonlarly, binuclear complexes with alkylidene bridges like ylbis(η 5 -cyclopentadienyl)(η 2 -propene)ditungsten(WϪW) (2B) [M 2 (η 5 -C 5 H 5 ) 2 (CO) 3 (µ-ethylidene)] (M ϭ Fe, Ru) react and the corresponding 1-butene complex (2C) can be isowith alkynes to the correspondingly substituted µ-η 1:3 -alklated and characterised by IR and 1 H-NMR spectroscopy.…”

Section: Discussionmentioning

confidence: 99%

Light-Induced Codimerisation of Acetylene and Olefins at a Binuclear Tungsten Complex

Kreiter¹,

Kern

Wolmershäuser

et al. 1998

Eur. J. Inorg. Chem.

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Section: Discussionmentioning

confidence: 99%

Light-Induced Codimerisation of Acetylene and Olefins at a Binuclear Tungsten Complex

Kreiter¹,

Kern

Wolmershäuser

et al. 1998

Eur. J. Inorg. Chem.

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“…For the previously reported μ-η 2 :η 2 - s - cis -butadiene complexes, the inner carbon atoms resonated at a lower magnetic field than the outer carbon atoms by ca. 20 ppm. − In contrast to the tendency, the 13 C signals derived from the inner and outer carbon atoms attached to the Cp*Ru fragment in 10c appeared oppositely. Namely, the outer 6 C atom appeared at δ 51.3, while the inner 5 C atom resonated at δ 43.5 ppm.…”

Section: Resultsmentioning

confidence: 88%

“…Insertion of ethylene into the Ru−C bond of a cationic μ-vinyl complex, [(CpRu) 2 (μ-η 2 -CH�CH 2 )(CO) 2 (MeCN)] + , yielding a μ-butadiene ligand has been elucidated by Knox and coworkers based on labeling experiments. 37 Deeming and coworkers demonstrated head-to-tail coupling of μ-vinyl groups in [Os 3 (μ-η 2 -CPh�CH 2 )(μ-η 2 -CH�CPhH)(μ 3 -S)(CO) 7] upon treatment with CO. 34 However, such a process was unlikely for I′.…”

Section: Synthesis Of Heterobimetallic Trihydrido Complexmentioning

confidence: 99%

Heterobimetallic Trihydrido Complex of Ruthenium and Rhodium Supported by Cyclopentadienyl Groups with Different Steric Demands

Takao,

Monoe,

Shimogawa

et al. 2023

Organometallics

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The reactivity of heterobimetallic trihydrido complexes of Ru and Rh supported by two kinds of cyclopentadienyl groups that provide steric differentiation in the dinuclear reaction field, [CpsRu(μ-H) 3 RhCps] (3b: CpsRu�Cp ‡ Ru, CpsRh�Cp*Rh, 3c: CpsRu� Cp*Ru, CpsRh�Cp ‡ Rh; Cp ‡ �1,2,4-t Bu 3 C 5 H 2 , Cp*�C 5 Me 5 ), was examined to elucidate the role of each metal center. Since the bulky Cp ‡ group on the Ru center in 3b retarded the uptake of diphenylacetylene, complex 3b reacted with diphenylacetylene at 60 °C to yield benzorhodacyclopentadiene complex 7b via the cyclometalation at the Rh center. In contrast, complex 3c, which contains a less congested Ru center, reacted with diphenylacetylene smoothly at 25 °C and afforded μ-alkenyl and μ-alkyne complexes, 5c and 6c. The rhodacyclopentadiene complex 7c was also obtained upon thermolysis of 6c but required heating at 180 °C. The reactivity toward acetylene did not differ from each other due to its high reactivity and μ-scis-η 2 :η 2 -butadiene-μ-vinyl complexes, 10b and 10c, were obtained. Although no intermediate was observed in the reaction, DFT calculations for a model compound supported by unsubstituted cyclopentadienyls suggested the exclusive uptake of acetylene at the Ru center. Complex 3b reacted with benzene at 25 °C under photo-irradiating conditions to yield μ-phenyl complex 11b in 52% yield, although 3c decomposed under the same conditions. The reason why a μ-phenyl complex was not formed in the photoreaction of 3c is that the Cp ‡ group on the Rh center suppressed the intramolecular migration of the phenyl group from the Ru to the Rh center. Instead, the decomposition induced by the coordination of additional benzene molecules to the Ru center was not suppressed. These results demonstrated that the Ru center acts as an initial binding site, although it is difficult to determine directly from the structure of the product.

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“…[49] from the alkenyl complex to the α-carbon atom of an inWith more reactive 1-alkynes (and in the absence of al-coming isocyanide (Scheme 15). [50] [54] kene), multiple alkyne insertions were observed.…”

Section: I32 Activation Of Alkynes and Vinyl-group Transfer Reactionsmentioning

confidence: 98%

Effects of Halides and Related Ligands on Reactions of Carbonylruthenium Complexes (Ru0–RuII)

Lavigne¹

1999

Eur. J. Inorg. Chem.

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While the primary motivation of fundamental studies on carbonylhalotriruthenium complexes was to understand the promoter effect of halides on certain ruthenium‐based catalytic systems of industrial relevance, such complexes have gained significance in their own right due to their remarkable ability to provide low‐activation energy pathways for the coordination of organic substrates. Limitations inherent to the fragility of these prototypes led to the design and development of a related family of more sophisticated derivatives where an aminopyridyl group serves as an alternate hemilabile ancillary ligand. Studies of their reactivity have revealed the possibility of achieving a number of stoichiometric or moderately catalytic “cluster‐mediated” transformations of organic substrates under very mild conditions. Yet, the viability of these systems is still limited to a narrow low‐energy domain. By contrast, halotriruthenium derivatives are still seen to function as catalyst precursors under the actual conditions of certain catalytic reactions where they act as sources of ruthenium(II) halide complexes that become the active components of the system. The second part of the review focuses on novel aspects of their fascinating chemistry.

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Synthesis of butadiene via vinyl–ethylene combination at a diruthenium centre

Abstract: Treatment of the p-vinyl cationtrans-b u t a d i e n e ; d e p rot o n at i o n is effected with KOH/ethanol to afford the neutral (S)-trans-butadiene complex [ R u ~( C O ) ~( ~-C H ~= C H C H = C H ~) ( ~-C5H5)2Im

Cited by 19 publications

References 8 publications

Light-Induced Codimerisation of Acetylene and Olefins at a Binuclear Tungsten Complex

Light-Induced Codimerisation of Acetylene and Olefins at a Binuclear Tungsten Complex

Heterobimetallic Trihydrido Complex of Ruthenium and Rhodium Supported by Cyclopentadienyl Groups with Different Steric Demands

Effects of Halides and Related Ligands on Reactions of Carbonylruthenium Complexes (Ru0–RuII)

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