Issue 12, 2023

Molybdate ionic liquids as halide-free catalysts for CO2 fixation into epoxides

Abstract

Herein we describe the syntheses of a series of molybdate and polyoxomolybdate ionic liquids (ILs), their full spectroscopic characterisation (FT-IR, 1H-, 13C-, 31P-, and 95Mo-NMR and ICP-MS), a comparison of their properties, and their applications as bifunctional catalysts for CO2 insertion into epoxides. The synthetic procedures to obtain ILs rely on anion exchange and acid–base reactions, including an innovative route for the synthesis of molybdate ionic liquids (Mo-ILs) using a halide-free organic IL precursor. The use of Mo-ILs as catalysts for CO2 fixation was investigated using 1,2-epoxyhexane as a model substrate. In the presence of 2.5 mol% of tetrabutylammonium molybdate, hexane carbonate was obtained in up to 86% yield at T = 120 °C, p0(CO2) = 30 bar in t = 9 h, under solventless conditions and without any added halide co-catalysts. The substrate scope was broadened to other 12 terminal and internal epoxides; moreover, the reaction was scaled up to 2 g of the substrate and catalyst recyclability was demonstrated up to 5 recycles.

Graphical abstract: Molybdate ionic liquids as halide-free catalysts for CO2 fixation into epoxides

Supplementary files

Article information

Article type
Paper
Submitted
24 Nov 2022
Accepted
16 Mai 2023
First published
18 Mai 2023
This article is Open Access
Creative Commons BY-NC license

Green Chem., 2023,25, 4849-4860

Molybdate ionic liquids as halide-free catalysts for CO2 fixation into epoxides

N. Bragato, A. Perosa, M. Selva, G. Fiorani and R. Calmanti, Green Chem., 2023, 25, 4849 DOI: 10.1039/D2GC04475G

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