A Hydrogen-Bonding Phosphonium/HFIP Catalyst for Efficient CO2 Conversion into Cyclic Carbonates
4 affiliations
- 1Universidad de Alicante , , P.O. Box 99, ,
- 2University of Almería , , Ctra. Sacramento s/n , ,
- 3Università di Salerno , , Via Ponte don Melillo , ,
- 4University of Camerino , , via Madonna delle Carceri , , ,
Abstract
Converting carbon dioxide (CO2) into carbonates is a promising strategy for mitigating carbon emissions. In this study, a series of phosphonium salts/hexafluoroisopropanol (HFIP) catalysts were synthesized and employed in the cycloaddition of CO2 to epoxides to produce cyclic carbonates under mild reaction conditions. The experimental results demonstrated that, at 25 °C and 1 atm CO2 pressure, the catalyst methyltriphenylphosphonium bromide/hexafluoroisopropanol 1/2 (Ph3MePBr/HFIP 1/2) achieved very high yields for monosubstituted (86–96%) as well as 1,1- and 1,2-disubstituted epoxides (66–88%). Density functional theory (DFT) calculations and NMR experiments were employed to elucidate the structure of the Ph3MePBr/HFIP 1/2 catalyst as well as the underlying reaction mechanism. The DFT mechanistic analysis indicated a hydrogen-bond-assisted SN2 pathway, in which the HFIP···Br– pair activates the epoxide and enables efficient CO2 fixation under mild conditions.
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BibTeX
@article{niguez2026hydrogenbonding,
title = {{A Hydrogen-Bonding Phosphonium/HFIP Catalyst for Efficient CO2 Conversion into Cyclic Carbonates}},
author = {Jose A. Ñíguez and Arantxa Forte-Castro and Michele Tomasini and Juana M. Pérez and Rafael Chinchilla and Matteo Tiecco and Ignacio Fernández and Laura Falivene and Diego A. Alonso},
journal = {ACS Omega},
year = {2026},
month = nov,
doi = {10.1021/acsomega.6c07310},
url = {https://pubs.acs.org/acsodf/article/doi/10.1021/acsomega.6c07310/5465186/A-Hydrogen-Bonding-Phosphonium-HFIP-Catalyst-for},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - A Hydrogen-Bonding Phosphonium/HFIP Catalyst for Efficient CO2 Conversion into Cyclic Carbonates
AU - Jose A. Ñíguez
AU - Arantxa Forte-Castro
AU - Michele Tomasini
AU - Juana M. Pérez
AU - Rafael Chinchilla
AU - Matteo Tiecco
AU - Ignacio Fernández
AU - Laura Falivene
AU - Diego A. Alonso
PY - 2026
DA - 2026/11/05
JO - ACS Omega
DO - 10.1021/acsomega.6c07310
UR - https://pubs.acs.org/acsodf/article/doi/10.1021/acsomega.6c07310/5465186/A-Hydrogen-Bonding-Phosphonium-HFIP-Catalyst-for
AB - Converting carbon dioxide (CO2) into carbonates is a promising strategy for mitigating carbon emissions. In this study, a series of phosphonium salts/hexafluoroisopropanol (HFIP) catalysts were synthesized and employed in the cycloaddition of CO2 to epoxides to produce cyclic carbonates under mild reaction conditions. The experimental results demonstrated that, at 25 °C and 1 atm CO2 pressure, the catalyst methyltriphenylphosphonium bromide/hexafluoroisopropanol 1/2 (Ph3MePBr/HFIP 1/2) achieved very high yields for monosubstituted (86–96%) as well as 1,1- and 1,2-disubstituted epoxides (66–88%). Density functional theory (DFT) calculations and NMR experiments were employed to elucidate the structure of the Ph3MePBr/HFIP 1/2 catalyst as well as the underlying reaction mechanism. The DFT mechanistic analysis indicated a hydrogen-bond-assisted SN2 pathway, in which the HFIP···Br– pair activates the epoxide and enables efficient CO2 fixation under mild conditions.
SN - 2470-1343
ER -