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Sökning: WFRF:(Lele S) > (2015)

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  • Wang, Ying, et al. (författare)
  • Alkene Epoxidation Catalysts [Ru(pdc)(tpy)] and [Ru(pdc)(pybox)] Revisited : Revealing a Unique Ru-IV=O Structure from a Dimethyl Sulfoxide Coordinating Complex
  • 2015
  • Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 5:7, s. 3966-3972
  • Tidskriftsartikel (refereegranskat)abstract
    • The X-ray crystal structure of a dimethyl sulfoxide (DMSO) coordinating complex [Ru-II(kappa(2)-pdc)(tpy)(DMSO)] (H(2)pdc = 2,6-pyridyl dicarboxylic acid and tpy = 2,2':6',2 ''-terpyridine) led to the discovery of a unique Ru-IV=O configuration for the Ru-pybox (pybox = pyridine-bis(oxazoline) ligands) epoxidation catalyst by theoretical calculations. On the basis of this structure, a detailed theoretical study was conducted on the alkene epoxidation reaction using ruthenium-based epoxidation catalysts. It was found that the process of H2O2 coordination proceeded via an associative path in which one carboxylate detached. The following H2O-elimination step was found to be facilitated by the detached carboxylate group. The resulting Ru-IV=O rearranges to the species trans-2a-oxo, in which one carboxylate group is situated over the tpy ring; the trans-2a-oxo was found to have the lowest activation free energies toward alkene epoxidation. These results demonstrated the importance of the hemilabile properties of the pdc(2-) ligand for the Ru-pdc alkene epoxidation catalysts.
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