[OSSO]-Type Iron(III) Complexes for the Low-Pressure Reaction of Carbon Dioxide with Epoxides: Catalytic Activity, Reaction Kinetics, and Computational Study

Francesco Della Monica, Bholanath Maity, Thomas Pehl, Antonio Buonerba, Assunta De Nisi, Magda Monari, Alfonso Grassi, Bernhard Rieger*, Luigi Cavallo, Carmine Capacchione

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

84 Scopus citations

Abstract

The 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).

Original languageEnglish (US)
Pages (from-to)6882-6893
Number of pages12
JournalACS Catalysis
Volume8
Issue number8
DOIs
StatePublished - Aug 3 2018

Bibliographical note

Funding Information:
Ministero 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.

Publisher Copyright:
Copyright © 2018 American Chemical Society.

Keywords

  • DFT
  • carbon dioxide
  • cycloaddition
  • iron
  • kinetics
  • mechanism
  • polymerization

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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