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Alkene Epoxidation Catalysts [Ru(pdc)(tpy)] and [Ru(pdc)(pybox)] Revisited: Revealing a Unique Ru-IV=O Structure from a Dimethyl Sulfoxide Coordinating Complex
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.ORCID iD: 0000-0003-1662-5817
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
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2015 (English)In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 5, no 7, 3966-3972 p.Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
2015. Vol. 5, no 7, 3966-3972 p.
Keyword [en]
epoxidation, ruthenium, DFT, hemilabile, oxidation, mechanism
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-171896DOI: 10.1021/acscatal.5b00496ISI: 000357626800008Scopus ID: 2-s2.0-84946130418OAI: oai:DiVA.org:kth-171896DiVA: diva2:845608
Funder
Swedish Research CouncilSwedish Energy AgencyKnut and Alice Wallenberg Foundation
Note

QC 20150812

Available from: 2015-08-12 Created: 2015-08-10 Last updated: 2017-12-04Bibliographically approved

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Duan, LeleSun, LichengAhlquist, Mårten S. G.

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