Reference : Synthesis and Catalytic Evaluation in Olefin Metathesis of a Second-Generation Homobi...
Scientific journals : Article
Physical, chemical, mathematical & earth Sciences : Chemistry
http://hdl.handle.net/2268/94085
Synthesis and Catalytic Evaluation in Olefin Metathesis of a Second-Generation Homobimetallic Ruthenium-Arene Complex Bearing a Vinylidene Ligand
English
Borguet, Yannick mailto [Université de Liège - ULg > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique]
Sauvage, Xavier [Université de Liège - ULg > > Centre de recherches du cyclotron]
Zaragoza, Guillermo [> > > >]
Demonceau, Albert mailto [Université de Liège - ULg > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique]
Delaude, Lionel mailto [Université de Liège - ULg > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique >]
2011
Organometallics
American Chemical Society
30
10
2730-2738
Yes (verified by ORBi)
International
0276-7333
1520-6041
Washington
DC
[en] The new homobimetallic ruthenium–vinylidene complex [(p-cymene)Ru(μ-Cl)3RuCl(═C═CHPh)(IMes)] (6) was isolated in high yield upon treatment of [(p-cymene)Ru(μ-Cl)3RuCl(η2-C2H4)(IMes)] (5) with a slight excess of phenylacetylene at −50 °C. Although it was very stable under normal atmosphere in the solid state, this product underwent an oxidative cleavage into the corresponding carbonyl compound [(p-cymene)Ru(μ-Cl)3RuCl(CO)(IMes)] (7) when dissolved in oxygen-containing solvents. Second-generation complexes 6 and 7 were characterized by IR and NMR spectroscopies, and their molecular structures were determined by X-ray diffraction analysis. The catalytic activity of complex 6 was probed in various types of olefin metathesis reactions. Compared to its first-generation analogue [(p-cymene)Ru(μ-Cl)3RuCl(═C═CHPh)(PCy3)], the new ruthenium initiator displayed an enhanced activity. It was also much more selective than ruthenium–ethylene complex 5. Aluminum chloride was a valuable cocatalyst for the ROMP of cyclooctene, whereas phenylacetylene was better suited to achieve the fast and quantitative RCM of α,ω-dienes into the corresponding di- or trisubstituted cycloolefins. The role of the terminal alkyne was rationalized by assuming that it would allow an enyne metathesis to take place, thereby transforming saturated vinylidene precursor 6 into a highly active mono- or bimetallic ruthenium–alkylidene species.
Researchers ; Professionals
http://hdl.handle.net/2268/94085
10.1021/om2001074

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