Coupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether-Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure-Reactivity Relationship and Mechanistic DFT Study

Handle URI:
http://hdl.handle.net/10754/622104
Title:
Coupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether-Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure-Reactivity Relationship and Mechanistic DFT Study
Authors:
Della Monica, Francesco; Vummaleti, Sai V. C. ( 0000-0001-7276-2475 ) ; Buonerba, Antonio; Nisi, Assunta De; Monari, Magda; Milione, Stefano; Grassi, Alfonso; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Capacchione, Carmine
Abstract:
A series of dinuclear iron(III)I complexes supported by thioether-triphenolate ligands have been prepared to attain highly Lewis acidic catalysts. In combination with tetrabutylammonium bromide (TBAB) they are highly active catalysts in the synthesis of cyclic organic carbonates through the coupling of carbon dioxide to epoxides with the highest initial turnover frequencies reported to date for the conversion of propylene oxide to propylene carbonate for iron-based catalysts (5200h-1; 120°C, 2MPa, 1h). In particular, these complexes are shown to be highly selective catalysts for the coupling of carbon dioxide to internal oxiranes affording the corresponding cyclic carbonates in good yield and with retention of the initial stereochemical configuration. A density functional theory (DFT) investigation provides a rational for the relative high activity found for these Fe(III) complexes, showing the fundamental role of the hemilabile sulfur atom in the ligand skeleton to promote reactivity. Notably, in spite of the dinuclear nature of the catalyst precursor only one metal center is involved in the catalytic cycle. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
KAUST Department:
KAUST Catalysis Center (KCC)
Citation:
Della Monica F, Vummaleti SVC, Buonerba A, Nisi AD, Monari M, et al. (2016) Coupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether-Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure-Reactivity Relationship and Mechanistic DFT Study. Advanced Synthesis & Catalysis 358: 3231–3243. Available: http://dx.doi.org/10.1002/adsc.201600621.
Publisher:
Wiley-Blackwell
Journal:
Advanced Synthesis & Catalysis
Issue Date:
25-Aug-2016
DOI:
10.1002/adsc.201600621
Type:
Article
ISSN:
1615-4150
Sponsors:
Financial support is acknowledged from the Ministero dell′Istruzione dell′Università e della Ricerca (MIUR, Roma, Italy for FARB 2015) and the SPRING cluster (REBIOCHEM research project CTN01 00063 49393). LC acknowledges the King Abdullah University of Science and Technology for supporting this research. The Centro di Tecnologie Integrate per la Salute (Project PONa3_00138) for the 600 MHz NMR instrumental time is acknowledged. The authors are also grateful to Dr. Guglielmo Monaco from University of Salerno for useful discussion, Dr. Patrizia Oliva and Dr. Patrizia Iannece from University of Salerno for technical assistance.
Is Supplemented By:
Monica, F. D., Vummaleti, S. V. C., Buonerba, A., De Nisi, A., Monari, M., Milione, S., … Capacchione, C. (2016). CCDC 1477580: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1lljwl; DOI:10.5517/ccdc.csd.cc1lljwl; HANDLE:http://hdl.handle.net/10754/624581
Additional Links:
http://onlinelibrary.wiley.com/doi/10.1002/adsc.201600621/full
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorDella Monica, Francescoen
dc.contributor.authorVummaleti, Sai V. C.en
dc.contributor.authorBuonerba, Antonioen
dc.contributor.authorNisi, Assunta Deen
dc.contributor.authorMonari, Magdaen
dc.contributor.authorMilione, Stefanoen
dc.contributor.authorGrassi, Alfonsoen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorCapacchione, Carmineen
dc.date.accessioned2017-01-01T13:18:22Z-
dc.date.available2017-01-01T13:18:22Z-
dc.date.issued2016-08-25en
dc.identifier.citationDella Monica F, Vummaleti SVC, Buonerba A, Nisi AD, Monari M, et al. (2016) Coupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether-Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure-Reactivity Relationship and Mechanistic DFT Study. Advanced Synthesis & Catalysis 358: 3231–3243. Available: http://dx.doi.org/10.1002/adsc.201600621.en
dc.identifier.issn1615-4150en
dc.identifier.doi10.1002/adsc.201600621en
dc.identifier.urihttp://hdl.handle.net/10754/622104-
dc.description.abstractA series of dinuclear iron(III)I complexes supported by thioether-triphenolate ligands have been prepared to attain highly Lewis acidic catalysts. In combination with tetrabutylammonium bromide (TBAB) they are highly active catalysts in the synthesis of cyclic organic carbonates through the coupling of carbon dioxide to epoxides with the highest initial turnover frequencies reported to date for the conversion of propylene oxide to propylene carbonate for iron-based catalysts (5200h-1; 120°C, 2MPa, 1h). In particular, these complexes are shown to be highly selective catalysts for the coupling of carbon dioxide to internal oxiranes affording the corresponding cyclic carbonates in good yield and with retention of the initial stereochemical configuration. A density functional theory (DFT) investigation provides a rational for the relative high activity found for these Fe(III) complexes, showing the fundamental role of the hemilabile sulfur atom in the ligand skeleton to promote reactivity. Notably, in spite of the dinuclear nature of the catalyst precursor only one metal center is involved in the catalytic cycle. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.en
dc.description.sponsorshipFinancial support is acknowledged from the Ministero dell′Istruzione dell′Università e della Ricerca (MIUR, Roma, Italy for FARB 2015) and the SPRING cluster (REBIOCHEM research project CTN01 00063 49393). LC acknowledges the King Abdullah University of Science and Technology for supporting this research. The Centro di Tecnologie Integrate per la Salute (Project PONa3_00138) for the 600 MHz NMR instrumental time is acknowledged. The authors are also grateful to Dr. Guglielmo Monaco from University of Salerno for useful discussion, Dr. Patrizia Oliva and Dr. Patrizia Iannece from University of Salerno for technical assistance.en
dc.publisherWiley-Blackwellen
dc.relation.urlhttp://onlinelibrary.wiley.com/doi/10.1002/adsc.201600621/fullen
dc.subjectCarbon dioxide fixationen
dc.subjectCycloadditionen
dc.subjectDensity functional theoryen
dc.subjectHomogeneous catalysisen
dc.subjectIronen
dc.titleCoupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether-Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure-Reactivity Relationship and Mechanistic DFT Studyen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalAdvanced Synthesis & Catalysisen
dc.contributor.institutionDipartimento di Chimica e Biologia “Adolfo Zambelli”; Università degli Studi di Salerno; via Giovanni Paolo II 84084 Fisciano (SA Italyen
dc.contributor.institutionInteruniversity Consortium Chemical Reactivity and Catalysis, CIRCC; via Celso Ulpiani 27 70126 Bari Italyen
dc.contributor.institutionDipartimento di Chimica G. Ciamician; Alma Mater Studiorum, Università di Bologna; via Selmi 2 40126 Bologna Italyen
kaust.authorVummaleti, Sai V. C.en
kaust.authorCavallo, Luigien
dc.relation.isSupplementedByMonica, F. D., Vummaleti, S. V. C., Buonerba, A., De Nisi, A., Monari, M., Milione, S., … Capacchione, C. (2016). CCDC 1477580: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1lljwlen
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1lljwlen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624581en
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.