Catalyst Decomposition during Olefin Metathesis Yields Isomerization-Active Ruthenium Nanoparticles
نویسندگان
چکیده
منابع مشابه
Prevention of undesirable isomerization during olefin metathesis.
1,4-Benzoquinones have been found to prevent olefin isomerization of a number of allylic ethers and long-chain aliphatic alkenes during ruthenium-catalyzed olefin metathesis reactions. Electron-deficient benzoquinones are the most effective additives for the prevention of olefin migration. This mild, inexpensive, and effective method to block olefin isomerization increases the synthetic utility...
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The success of enantioselective olefin metathesis relies on the design of enantioenriched alkylidene complexes capable of transferring stereochemical information from the catalyst structure to the reactants. Cyclometalation of the NHC ligand has proven to be a successful strategy to incorporate stereogenic atoms into the catalyst structure. Enantioenriched complexes incorporating this design el...
متن کاملKey processes in ruthenium-catalysed olefin metathesis.
While the fundamental series of [2+2]cycloadditions and retro[2+2]cycloadditions that make up the pathways of ruthenium-catalysed metathesis reactions is well-established, the exploration of mechanistic aspects of alkene metathesis continues. In this Feature Article, modern mechanistic studies of the alkene metathesis reaction, catalysed by well-defined ruthenium complexes, are discussed. Broad...
متن کاملThe isomerization equilibrium between cis and trans chloride ruthenium olefin metathesis catalysts from quantum mechanics calculations.
The cis-trans chloride isomerization of a ruthenium olefin metathesis catalyst is studied using quantum mechanics (B3LYP DFT), including the Poisson-Boltzmann (PBF) continuum approximation. The predicted geometries agree with experiment. The energies in methylene chloride, lead to DeltaG = -0.70 kcal/mol and a cis:trans ratio of 76:24, quite close to the experimental value of DeltaG = -0.78 kca...
متن کاملDecomposition of a key intermediate in ruthenium-catalyzed olefin metathesis reactions.
Dinuclear ruthenium complex, with a bridging carbide and a hydride ligand, and methyltricyclohexylphosphonium chloride result from thermal decomposition of olefin metathesis catalyst, (IMesH2)(PCy3)(Cl)2Ru=CH2. Involvement of dissociated phosphine in the decomposition is proposed. The dinuclear complex has catalytic olefin isomerization activity, which can be responsible for competing isomeriza...
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ژورنال
عنوان ژورنال: ChemCatChem
سال: 2016
ISSN: 1867-3880
DOI: 10.1002/cctc.201600890