Simple and cheap steric and electronic characterization of the reactivity of Ru(II) complexes containing oxazoline ligands as epoxidation catalysts

Handle URI:
http://hdl.handle.net/10754/562839
Title:
Simple and cheap steric and electronic characterization of the reactivity of Ru(II) complexes containing oxazoline ligands as epoxidation catalysts
Authors:
Poater, Albert; Falivene, Laura; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Llobet, Antoni A.; Rodríguez, Montserrat Carmen Ríos; Romero, Isabel; Solà, Miquel
Abstract:
The reactivity of a new family of complexes with general formula [Ru IV(T)(R-D)(O)]2+ (T = trispyrazolylmethane (tpm); D = N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4, 5-dihydrooxazole-2-carbimidate, R = Bz (1); iPr (2)) has been analyzed. There is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; 1 leads to the regioselective oxidation at the ring alkene position, whereas 2 leads to the oxidation at the terminal position. Although computational calculations indicate small energy differences, both the geometry through steric maps and the electronic parameters of the reactants via conceptual DFT, or charges via NPA, explain the reactivity differences found for the catalysts depending on the substituents of the oxazoline ligands. © 2013 Elsevier B.V. All rights reserved.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
Elsevier BV
Journal:
Chemical Physics Letters
Issue Date:
Jul-2013
DOI:
10.1016/j.cplett.2013.05.032
Type:
Article
ISSN:
00092614
Sponsors:
We acknowledge financial support from the MICINN of Spain (CTQ2007-60476/PPQ to I. R and M. R. and CTQ2011-23156/BQU to M. S.), the DIUE of the Generalitat de Catalunya (projects 2009SGR637 and Xarxa de Referencia en Quimica Teorica i Computacional), and the European Fund for Regional Development fund for the grant UNGI08-4E-003. M. S. is also grateful to the DIUE of the Generalitat de Catalunya for financial help through the ICREA Academia 2009 prize for excellence in research. A. P. thanks MICINN for a Ramon y Cajal contract (RYC-2009-05226), European Commission for a Career Integration Grant (CIG09-GA-2011-293900), and Generalitat de Catalunya (2012BE100824). Johnson & Matthey LTD are acknowledged for a RuCl<INF>3</INF>center dot nH<INF>2</INF>O loan. We also thank Centre de Supercomputacio de Catalunya (CESCA) for partial funding of computer time. The authors are extremely thankful for the helpful comments and assistance of Dr. Francesco Ragone.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorPoater, Alberten
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorLlobet, Antoni A.en
dc.contributor.authorRodríguez, Montserrat Carmen Ríosen
dc.contributor.authorRomero, Isabelen
dc.contributor.authorSolà, Miquelen
dc.date.accessioned2015-08-03T11:12:13Zen
dc.date.available2015-08-03T11:12:13Zen
dc.date.issued2013-07en
dc.identifier.issn00092614en
dc.identifier.doi10.1016/j.cplett.2013.05.032en
dc.identifier.urihttp://hdl.handle.net/10754/562839en
dc.description.abstractThe reactivity of a new family of complexes with general formula [Ru IV(T)(R-D)(O)]2+ (T = trispyrazolylmethane (tpm); D = N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4, 5-dihydrooxazole-2-carbimidate, R = Bz (1); iPr (2)) has been analyzed. There is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; 1 leads to the regioselective oxidation at the ring alkene position, whereas 2 leads to the oxidation at the terminal position. Although computational calculations indicate small energy differences, both the geometry through steric maps and the electronic parameters of the reactants via conceptual DFT, or charges via NPA, explain the reactivity differences found for the catalysts depending on the substituents of the oxazoline ligands. © 2013 Elsevier B.V. All rights reserved.en
dc.description.sponsorshipWe acknowledge financial support from the MICINN of Spain (CTQ2007-60476/PPQ to I. R and M. R. and CTQ2011-23156/BQU to M. S.), the DIUE of the Generalitat de Catalunya (projects 2009SGR637 and Xarxa de Referencia en Quimica Teorica i Computacional), and the European Fund for Regional Development fund for the grant UNGI08-4E-003. M. S. is also grateful to the DIUE of the Generalitat de Catalunya for financial help through the ICREA Academia 2009 prize for excellence in research. A. P. thanks MICINN for a Ramon y Cajal contract (RYC-2009-05226), European Commission for a Career Integration Grant (CIG09-GA-2011-293900), and Generalitat de Catalunya (2012BE100824). Johnson & Matthey LTD are acknowledged for a RuCl<INF>3</INF>center dot nH<INF>2</INF>O loan. We also thank Centre de Supercomputacio de Catalunya (CESCA) for partial funding of computer time. The authors are extremely thankful for the helpful comments and assistance of Dr. Francesco Ragone.en
dc.publisherElsevier BVen
dc.titleSimple and cheap steric and electronic characterization of the reactivity of Ru(II) complexes containing oxazoline ligands as epoxidation catalystsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalChemical Physics Lettersen
dc.contributor.institutionDepartament de Química, Institut de Química Computacional i Catàlisi (IQCC), Universitat de Girona, E-17071 Girona, Spainen
dc.contributor.institutionCatalan Institute for Water Research (ICRA), H2O Building, University of Girona, Emili Grahit 101, E-17003 Girona, Spainen
dc.contributor.institutionDepartment of Chemistry and Biology, University of Salerno, Via Ponte don Melillo, Fisciano I-84084, Italyen
dc.contributor.institutionDepartament de Química, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, E-08193 Barcelona, Spainen
dc.contributor.institutionInstitute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, E-43007 Tarragona, Spainen
kaust.authorCavallo, Luigien
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.