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

Francesco Della Monica, Sai V. C. Vummaleti, Antonio Buonerba, Assunta De Nisi, Magda Monari, Stefano Milione, Alfonso Grassi, Luigi Cavallo, Carmine Capacchione

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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.
Original languageEnglish (US)
Pages (from-to)3231-3243
Number of pages13
JournalAdvanced Synthesis & Catalysis
Volume358
Issue number20
DOIs
StatePublished - Aug 25 2016

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: 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.

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