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dc.contributor.authorDella Monica, Francesco
dc.contributor.authorMaity, Bholanath
dc.contributor.authorPehl, Thomas
dc.contributor.authorBuonerba, Antonio
dc.contributor.authorDe Nisi, Assunta
dc.contributor.authorMonari, Magda
dc.contributor.authorGrassi, Alfonso
dc.contributor.authorRieger, Bernhard
dc.contributor.authorCavallo, Luigi
dc.contributor.authorCapacchione, Carmine
dc.date.accessioned2019-10-08T14:05:18Z
dc.date.available2019-10-08T14:05:18Z
dc.date.issued2018-06-15
dc.identifier.citationDella Monica, F., Maity, B., Pehl, T., Buonerba, A., De Nisi, A., Monari, M., … Capacchione, C. (2018). [OSSO]-Type Iron(III) Complexes for the Low-Pressure Reaction of Carbon Dioxide with Epoxides: Catalytic Activity, Reaction Kinetics, and Computational Study. ACS Catalysis, 8(8), 6882–6893. doi:10.1021/acscatal.8b01695
dc.identifier.doi10.1021/acscatal.8b01695
dc.identifier.urihttp://hdl.handle.net/10754/658564
dc.description.abstractThe selective conversion of variously substituted epoxides into the corresponding cyclic carbonates under mild reaction conditions was achieved with mononuclear Fe(III) complexes bearing bis-thioether-diphenolate [OSSO]-type ligands, in combination with tetrabutylammonium bromide (TBAB). For example, propylene carbonate was obtained in 1 h at 35 °C (turnover frequency, TOF = 290 h-1), from propylene oxide and 1 bar of CO2 pressure, using 0.1 mol % of the Fe(III) complex and 0.5 mol % of TBAB. Product divergence is observed only for cyclohexene oxide toward the exclusive formation of the aliphatic polycarbonate (TOF = 165 h-1 at 80 °C and 1 bar of CO2 pressure, using 0.1 mol % of the Fe(III) complex and 0.1 mol % of tetrabutylammonium chloride). Kinetic investigations indicated reaction orders of two and one, with respect to the Fe(III) complex, for the production of propylene carbonate and the poly(cyclohexene carbonate), respectively. The enthalpy and entropy of activation were determined using the Eyring equation [for propylene carbonate: δH‡ = 8.4 ± 0.7 kcal/mol and δS‡ = -33 ± 3 cal/(mol·K); for poly(cyclohexene carbonate): δH‡ = 11.9 ± 0.3 kal/mol and δS‡ = -36 ± 2.2 cal/(mol·K)]. Supported by density functional theory based investigations, we propose a mechanistic scenario in which the rate-limiting step is the bimetallic ring opening of the epoxide, in the case of propylene carbonate, and the monometallic insertion of the epoxide in the growing polymer chain, in the case of poly(cyclohexene carbonate).
dc.description.sponsorshipMinistero dell’Istruzione dell’Università e della Ricerca (MIUR, Roma, Italy) and Università degli Studi di Salerno (FARB 2016-ORSA165551), the Centro di Tecnologie Integrate per la Salute (Project PONa3_00138) for the 600 MHz NMR instrumental time, Salvatore Impemba, Dr. Patrizia Oliva, Dr. Patrizia Iannece, Dr. Mariagrazia Napoli, and Dr. Ivano Immediata from University of Salerno for technical assistance are deeply acknowledged. C.C. thanks the Alexander von Humboldt foundation for financial support. L.C. and B.M. thank the King Abdullah University of Science and Technology for supporting this research.
dc.language.isoen
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/acscatal.8b01695
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/10.1021/acscatal.8b01695.
dc.subjectcarbon dioxide
dc.subjectcycloaddition
dc.subjectDFT
dc.subjectiron
dc.subjectkinetics
dc.subjectmechanism
dc.subjectpolymerization
dc.title[OSSO]-Type Iron(III) Complexes for the Low-Pressure Reaction of Carbon Dioxide with Epoxides: Catalytic Activity, Reaction Kinetics, and Computational Study
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalACS Catalysis
dc.rights.embargodate2019-06-15
dc.eprint.versionPost-print
dc.contributor.institutionDipartimento di Chimica e Biologia “Adolfo Zambelli”, Università degli Studi di Salerno, Via Giovanni Paolo II, 84084 Fisciano, SA, Italy
dc.contributor.institutionWACKER-Lehrstuhl für Makromolekulare Chemie, Zentralinstitut für Katalyseforschung (CRC), Technische Universitat München, Lichtenbergstraße 4, 85747 Garching, Germany
dc.contributor.institutionDipartimento di Chimica G. Ciamician, Alma Mater Studiorum, Università di Bologna, via Selmi 2, 40126 Bologna, Italy
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)
pubs.publication-statusPublished
kaust.personMaity, Bholanath
kaust.personCavallo, Luigi
refterms.dateFOA2019-10-08T14:05:19Z
display.relations<b> Is Supplemented By:</b> <br/> <ul> <li><i>[Dataset]</i> <br/> . DOI: <a href="https://doi.org/10.5517/ccdc.csd.cc1phqws">10.5517/ccdc.csd.cc1phqws</a> HANDLE: <a href="http://hdl.handle.net/10754/664786">10754/664786</a></li></ul>
dc.date.published-online2018-06-15
dc.date.published-print2018-08-03


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