The synthesis and characterization of three new bis-thioether-phenolate monoanionic tridentate [SOS]-type ligands, and the synthesis of the corresponding Fe(II) and Fe(III) complexes are reported. Their application, in combination with tetrabutylammonium bromide (TBAB), as catalysts for the cycloaddition of CO2to a number of monosubstituted epoxides and cyclohexene oxide was investigated. For example, epichlorohydrin is converted in the corresponding cyclic carbonate, with a turnover frequency of 155 h−1(0.1 mol% of iron, 0.5 mol% of TBAB, 10 bar of CO2). With the aim to obtain further information about the catalyst structure-activity relationship and the reaction mechanism, the reaction between the catalyst precursors and TBAB was investigated, suggesting the formation of an anionic metallate species in the case of the Fe(III) complexes that is supposed to be true catalyst. A mechanistic scenario explaining the different behaviour of the Fe(II) and Fe(III) complexes is proposed.

CO2cycloaddition to epoxides promoted by bis-thioether-phenolate Fe(II) and Fe(III) complexes

Della Monica, Francesco;
2018-01-01

Abstract

The synthesis and characterization of three new bis-thioether-phenolate monoanionic tridentate [SOS]-type ligands, and the synthesis of the corresponding Fe(II) and Fe(III) complexes are reported. Their application, in combination with tetrabutylammonium bromide (TBAB), as catalysts for the cycloaddition of CO2to a number of monosubstituted epoxides and cyclohexene oxide was investigated. For example, epichlorohydrin is converted in the corresponding cyclic carbonate, with a turnover frequency of 155 h−1(0.1 mol% of iron, 0.5 mol% of TBAB, 10 bar of CO2). With the aim to obtain further information about the catalyst structure-activity relationship and the reaction mechanism, the reaction between the catalyst precursors and TBAB was investigated, suggesting the formation of an anionic metallate species in the case of the Fe(III) complexes that is supposed to be true catalyst. A mechanistic scenario explaining the different behaviour of the Fe(II) and Fe(III) complexes is proposed.
2018
2018
http://www.elsevier.com/locate/issn/24688231
Carbon dioxide; Cyclic organic carbonate; Epoxide; Homogeneous catalysis; Iron; Catalysis; Process Chemistry and Technology; Physical and Theoretical Chemistry
Della Monica, Francesco; Leone, Mattia; Buonerba, Antonio; Grassi, Alfonso; Milione, Stefano; Capacchione, Carmine
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11383/2129316
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