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Light-driven reduction of CO2: thermodynamics and kinetics of hydride transfer reactions in benzimidazoline derivatives

Authorized Users Only
2022
Authors
Ostojić, Bojana
Stanković, Branislav
Đorđević, Dragana
Schwerdtfeger, Peter
Article (Published version)
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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 / Hydrosilylation
Source:
Physical Chemistry Chemical Physics, 2022, 24, 34, 20357-20370
Publisher:
  • Elsevier
Funding / projects:
  • Ministry of Education, Science and Technological Development, Republic of Serbia, Grant no. 200026 (University of Belgrade, Institute of Chemistry, Technology and Metallurgy - IChTM) (RS-200026)

DOI: 10.1039/d2cp02867k

ISSN: 1463-9076; 1463-9084

PubMed: 35980288

WoS: 000841524900001

Scopus: 2-s2.0-85136857916
[ Google Scholar ]
URI
https://cer.ihtm.bg.ac.rs/handle/123456789/5350
Collections
  • Radovi istraživača / Researchers' publications
Institution/Community
IHTM
TY  - 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 . .

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