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dc.contributor.authorDi Giovanni, Carlo
dc.contributor.authorPoater, Albert
dc.contributor.authorBenet-Buchholz, Jordi
dc.contributor.authorCavallo, Luigi
dc.contributor.authorSolà, Miquel
dc.contributor.authorLlobet, Antoni A.
dc.date.accessioned2015-08-03T11:51:15Z
dc.date.available2015-08-03T11:51:15Z
dc.date.issued2014-03-03
dc.identifier.citationDi Giovanni, C., Poater, A., Benet-Buchholz, J., Cavallo, L., Solà, M., & Llobet, A. (2014). Dinuclear Ru-Aqua Complexes for Selective Epoxidation Catalysis Based on Supramolecular Substrate Orientation Effects. Chemistry - A European Journal, 20(14), 3898–3902. doi:10.1002/chem.201304699
dc.identifier.issn09476539
dc.identifier.doi10.1002/chem.201304699
dc.identifier.urihttp://hdl.handle.net/10754/563429
dc.description.abstractRu-aqua complex {[RuII(trpy)(H2O)] 2(μ-pyr-dc)}+ is a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes. High turnover numbers (TNs), up to 17000, and turnover frequencies (TOF), up to 24120 h-1 (6.7 s -1), have been obtained using PhIO as oxidant. This species presents an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides. In addition, it shows different reactivity to cis and trans olefins due to a substrate orientation supramolecular effect transmitted by its ligand scaffold. This effect together with the impressive reaction rates are rationalized using electrochemical techniques and DFT calculations. A new Ru-aqua complex that behaves as a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes is reported. High turnover numbers and frequencies are obtained by using PhIO as oxidant. The complex shows an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides (see figure). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
dc.description.sponsorshipThis research was supported financially by MINECO (CTQ2011-23156/BQU, CTQ2010-21497 and PRI-PIBIN-2011-1278), ICIQ, FEDER fund (UNGI08-4E-003), ICREA Academia, Generalitat de Catalunya (2009SGR637); Ramon y Cajal contract (RYC-2009-05226) of MINECO, and Career Integration Grant (CIG09-GA-2011-293900) of the European Commission. COST Actions CM1205 and CM1202 are also gratefully acknowledged.
dc.publisherWiley
dc.subjectdensity functional calculations
dc.subjectelectrochemistry
dc.subjectepoxidation
dc.subjectruthenium
dc.subjectsupramolecular redox catalysis
dc.titleDinuclear ru-aqua complexes for selective epoxidation catalysis based on supramolecular substrate orientation effects
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalChemistry - A European Journal
dc.contributor.institutionInstitute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Spain
dc.contributor.institutionDepartament de Química, Universitat Autònoma de Barcelona Cerdanyola Del Vallès, 08193, Barcelona, Spain
dc.contributor.institutionInstitut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, 17071 Girona, Spain
kaust.personCavallo, Luigi
dc.relation.issupplementedbyDOI:10.5517/cc1jz9mf
display.relations<b> Is Supplemented By:</b> <br/> <ul><li><i>[Dataset]</i> <br/> Di Giovanni, C., Poater, A., Benet-Buchholz, J., Cavallo, L., Sola, M., & Llobet, A. (2015). CCDC 1429305: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jz9mf. DOI: <a href="https://doi.org/10.5517/cc1jz9mf">10.5517/cc1jz9mf</a> HANDLE: <a href="http://hdl.handle.net/10754/624475">10754/624475</a></li></ul>
dc.date.published-online2014-03-03
dc.date.published-print2014-04-01


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