DFT Study of Halide‐Free Mechanism of the CO2 Cycloaddition onto Epoxide by [PW11O39{Zn(H2O)}]5−: Evidences for the Formation of Hydrogencarbonate Intermediates

• Published in: ChemCatChem Vol. 17; no. 15
• Main Authors: Ren, Jingjing, Launay, Franck, Villanneau, Richard, Gérard, Hélène
• Format: Journal Article
• Language: English
• Published: 07.08.2025
• Subjects: CO2 activation; Cyclic carbonate; DFT calculation; Polyoxometalate; Zinc
• ISSN: 1867-3880; 1867-3899
• DOI: 10.1002/cctc.202500312

The intertwined experimental and theoretical study of the reaction of CO2 with styrene oxide in the presence of the tetraoctylammonium salt of [PW11O39ZnII(H2O)]5− evidences the carbonic anhydrase‐like role of the polyoxometalate center in catalyzing the reaction. We computationally propose a reaction pathway involving the transient formation of an HCO3− moiety involved in the stepwise conversion of the epoxide into a cyclic carbonate. These calculations enabled us to improve the catalytic reactivity of these polyoxometalates by introducing HCO3− as a co‐catalyst in the cycloaddition reactions of CO2 on a variety of epoxides. The computational study, sustained by experimental data, of the catalytic activity of [PW11O39{Zn(H2O)}]5− in CO2 cycloaddition to epoxide highlights how the carbonic anhydrase‐like character of this complex couples to the versatile binding properties of the polyoxometalate in this reaction pathway.