Light-driven reduction of CO2: thermodynamics and kinetics of hydride transfer reactions in benzimidazoline derivatives
Abstract
CO2 capture, conversion and storage belong to the holy grail of environmental science. We therefore explore an important photochemical hydride transfer reaction of benzimidazoline derivatives with CO2 in a polar solvent (dimethylsulfoxide) by quantum-chemical methods. While the excited electronic state undergoing hydride transfer to formate (HCOO−) shows a higher reaction path barrier compared to the ground state, a charge-transfer can occur in the near-UV region with nearly barrierless access to the products involving a conical intersection between both electronic states. Such radiationless decay through the hydride transfer reaction and formation of HCCO−via excited electronic states in suitable organic compounds opens the way for future photochemical CO2 reduction. We provide a detailed analysis for the chemical CO2 reduction to the formate anion for 15 different benzimidazoline derivatives in terms of thermodynamic hydricities (ΔGH), activation free energies (ΔG‡HT), and reaction f...ree energies (ΔGrxn) for the chosen solvent dimethylsulfoxide at the level of density functional theory. The calculated hydricities are in the range from 35.0 to 42.0 kcal mol−1i.e. the species possess strong hydride donor abilities required for the CO2 reduction to formate, characterized by relatively low activation free energies between 18.5 and 22.2 kcal mol−1. The regeneration of the benzimidazoline can be achieved electrochemically.
Keywords:
Carbon-dioxide fixation / Frustrated lewis pair / Density functionals / Proton transfer / TD-DFT / Methanol / Thermochemistry / HydrosilylationSource:
Physical Chemistry Chemical Physics, 2022, 24, 34, 20357-20370Publisher:
- Elsevier
Funding / projects:
DOI: 10.1039/d2cp02867k
ISSN: 1463-9076; 1463-9084
PubMed: 35980288
WoS: 000841524900001
Scopus: 2-s2.0-85136857916
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Institution/Community
IHTMTY - JOUR AU - Ostojić, Bojana AU - Stanković, Branislav AU - Đorđević, Dragana AU - Schwerdtfeger, Peter PY - 2022 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/5350 AB - CO2 capture, conversion and storage belong to the holy grail of environmental science. We therefore explore an important photochemical hydride transfer reaction of benzimidazoline derivatives with CO2 in a polar solvent (dimethylsulfoxide) by quantum-chemical methods. While the excited electronic state undergoing hydride transfer to formate (HCOO−) shows a higher reaction path barrier compared to the ground state, a charge-transfer can occur in the near-UV region with nearly barrierless access to the products involving a conical intersection between both electronic states. Such radiationless decay through the hydride transfer reaction and formation of HCCO−via excited electronic states in suitable organic compounds opens the way for future photochemical CO2 reduction. We provide a detailed analysis for the chemical CO2 reduction to the formate anion for 15 different benzimidazoline derivatives in terms of thermodynamic hydricities (ΔGH), activation free energies (ΔG‡HT), and reaction free energies (ΔGrxn) for the chosen solvent dimethylsulfoxide at the level of density functional theory. The calculated hydricities are in the range from 35.0 to 42.0 kcal mol−1i.e. the species possess strong hydride donor abilities required for the CO2 reduction to formate, characterized by relatively low activation free energies between 18.5 and 22.2 kcal mol−1. The regeneration of the benzimidazoline can be achieved electrochemically. PB - Elsevier T2 - Physical Chemistry Chemical Physics T1 - Light-driven reduction of CO2: thermodynamics and kinetics of hydride transfer reactions in benzimidazoline derivatives VL - 24 IS - 34 SP - 20357 EP - 20370 DO - 10.1039/d2cp02867k ER -
@article{ author = "Ostojić, Bojana and Stanković, Branislav and Đorđević, Dragana and Schwerdtfeger, Peter", year = "2022", abstract = "CO2 capture, conversion and storage belong to the holy grail of environmental science. We therefore explore an important photochemical hydride transfer reaction of benzimidazoline derivatives with CO2 in a polar solvent (dimethylsulfoxide) by quantum-chemical methods. While the excited electronic state undergoing hydride transfer to formate (HCOO−) shows a higher reaction path barrier compared to the ground state, a charge-transfer can occur in the near-UV region with nearly barrierless access to the products involving a conical intersection between both electronic states. Such radiationless decay through the hydride transfer reaction and formation of HCCO−via excited electronic states in suitable organic compounds opens the way for future photochemical CO2 reduction. We provide a detailed analysis for the chemical CO2 reduction to the formate anion for 15 different benzimidazoline derivatives in terms of thermodynamic hydricities (ΔGH), activation free energies (ΔG‡HT), and reaction free energies (ΔGrxn) for the chosen solvent dimethylsulfoxide at the level of density functional theory. The calculated hydricities are in the range from 35.0 to 42.0 kcal mol−1i.e. the species possess strong hydride donor abilities required for the CO2 reduction to formate, characterized by relatively low activation free energies between 18.5 and 22.2 kcal mol−1. The regeneration of the benzimidazoline can be achieved electrochemically.", publisher = "Elsevier", journal = "Physical Chemistry Chemical Physics", title = "Light-driven reduction of CO2: thermodynamics and kinetics of hydride transfer reactions in benzimidazoline derivatives", volume = "24", number = "34", pages = "20357-20370", doi = "10.1039/d2cp02867k" }
Ostojić, B., Stanković, B., Đorđević, D.,& Schwerdtfeger, P.. (2022). Light-driven reduction of CO2: thermodynamics and kinetics of hydride transfer reactions in benzimidazoline derivatives. in Physical Chemistry Chemical Physics Elsevier., 24(34), 20357-20370. https://doi.org/10.1039/d2cp02867k
Ostojić B, Stanković B, Đorđević D, Schwerdtfeger P. Light-driven reduction of CO2: thermodynamics and kinetics of hydride transfer reactions in benzimidazoline derivatives. in Physical Chemistry Chemical Physics. 2022;24(34):20357-20370. doi:10.1039/d2cp02867k .
Ostojić, Bojana, Stanković, Branislav, Đorđević, Dragana, Schwerdtfeger, Peter, "Light-driven reduction of CO2: thermodynamics and kinetics of hydride transfer reactions in benzimidazoline derivatives" in Physical Chemistry Chemical Physics, 24, no. 34 (2022):20357-20370, https://doi.org/10.1039/d2cp02867k . .