Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution
Authors
Milovanović, Milan R.![](/themes/MirageCherry/images/orcid.png)
Dherbassy, Quentin
Wencel-Delord, Joanna
Colobert, Françoise
Zarić, Snežana D.
![](/themes/MirageCherry/images/orcid.png)
Djukic, Jean-Pierre
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HFIP, i.e. 1,1,1,3,3,3-hexafluoropropan-2-ol, was found to be an exceptional medium,[1] either as solvent or co-solvent, that allows many reactions to occur.[2-5] However, the exact role and mode of action of HFIP in various chemical transformations still remains elusive. Despite many reports dealing with water/HFIP complexes, little has been published on other molecular complexes of HFIP as well as on thermochemistry of the formation of such complexes.[6]
Within this study the affinity of a series of eight different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) to HFIP (as Lewis acid) is investigated
experimentally by Isothermal Titration Calorimetry (ITC) and theoretically using static DFT-D calculations. Measured ITC association enthalpy values ΔHaITC spanned -9.3 kcal/mol - -14
kcal/mol. Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems - ΔHa values ran...ging -8.5 – -12.7 kcal/mol. In general, most of interaction energy is due to the hydrogen bonding and not due to formation of significantly strong halogen bonds. An additional set of calculations combining implicit and explicit solvation by chlorobenzene of the reactants, pointed out the relatively low interference of the solvent with the HFIPbase complexation, which main effect is to slightly enhance the Gibbs energy of the HFIP-Lewis base association. It is speculated that the interactions of bulk HFIP with Lewis bases therefore may significantly intervene in catalytic processes not only via the dynamic miscrostructuration of the medium but also more explicitly by affecting bonds’ polarization at the Lewis bases.
Source:
The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020, 2020, 161-161Funding / projects:
- ANR-DFG project COCOORDCHEM
- Noncovalent interactions of pi-systems and their role in molecular recognition (RS-MESTD-Basic Research (BR or ON)-172065)
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Inovacioni centar / Innovation CentreTY - CONF AU - Milovanović, Milan R. AU - Dherbassy, Quentin AU - Wencel-Delord, Joanna AU - Colobert, Françoise AU - Zarić, Snežana D. AU - Djukic, Jean-Pierre PY - 2020 UR - http://cherry.chem.bg.ac.rs/handle/123456789/6357 AB - HFIP, i.e. 1,1,1,3,3,3-hexafluoropropan-2-ol, was found to be an exceptional medium,[1] either as solvent or co-solvent, that allows many reactions to occur.[2-5] However, the exact role and mode of action of HFIP in various chemical transformations still remains elusive. Despite many reports dealing with water/HFIP complexes, little has been published on other molecular complexes of HFIP as well as on thermochemistry of the formation of such complexes.[6] Within this study the affinity of a series of eight different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) to HFIP (as Lewis acid) is investigated experimentally by Isothermal Titration Calorimetry (ITC) and theoretically using static DFT-D calculations. Measured ITC association enthalpy values ΔHaITC spanned -9.3 kcal/mol - -14 kcal/mol. Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems - ΔHa values ranging -8.5 – -12.7 kcal/mol. In general, most of interaction energy is due to the hydrogen bonding and not due to formation of significantly strong halogen bonds. An additional set of calculations combining implicit and explicit solvation by chlorobenzene of the reactants, pointed out the relatively low interference of the solvent with the HFIPbase complexation, which main effect is to slightly enhance the Gibbs energy of the HFIP-Lewis base association. It is speculated that the interactions of bulk HFIP with Lewis bases therefore may significantly intervene in catalytic processes not only via the dynamic miscrostructuration of the medium but also more explicitly by affecting bonds’ polarization at the Lewis bases. C3 - The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020 T1 - Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution SP - 161 EP - 161 UR - https://hdl.handle.net/21.15107/rcub_cherry_6357 ER -
@conference{ author = "Milovanović, Milan R. and Dherbassy, Quentin and Wencel-Delord, Joanna and Colobert, Françoise and Zarić, Snežana D. and Djukic, Jean-Pierre", year = "2020", abstract = "HFIP, i.e. 1,1,1,3,3,3-hexafluoropropan-2-ol, was found to be an exceptional medium,[1] either as solvent or co-solvent, that allows many reactions to occur.[2-5] However, the exact role and mode of action of HFIP in various chemical transformations still remains elusive. Despite many reports dealing with water/HFIP complexes, little has been published on other molecular complexes of HFIP as well as on thermochemistry of the formation of such complexes.[6] Within this study the affinity of a series of eight different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) to HFIP (as Lewis acid) is investigated experimentally by Isothermal Titration Calorimetry (ITC) and theoretically using static DFT-D calculations. Measured ITC association enthalpy values ΔHaITC spanned -9.3 kcal/mol - -14 kcal/mol. Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems - ΔHa values ranging -8.5 – -12.7 kcal/mol. In general, most of interaction energy is due to the hydrogen bonding and not due to formation of significantly strong halogen bonds. An additional set of calculations combining implicit and explicit solvation by chlorobenzene of the reactants, pointed out the relatively low interference of the solvent with the HFIPbase complexation, which main effect is to slightly enhance the Gibbs energy of the HFIP-Lewis base association. It is speculated that the interactions of bulk HFIP with Lewis bases therefore may significantly intervene in catalytic processes not only via the dynamic miscrostructuration of the medium but also more explicitly by affecting bonds’ polarization at the Lewis bases.", journal = "The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020", title = "Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution", pages = "161-161", url = "https://hdl.handle.net/21.15107/rcub_cherry_6357" }
Milovanović, M. R., Dherbassy, Q., Wencel-Delord, J., Colobert, F., Zarić, S. D.,& Djukic, J.. (2020). Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution. in The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020, 161-161. https://hdl.handle.net/21.15107/rcub_cherry_6357
Milovanović MR, Dherbassy Q, Wencel-Delord J, Colobert F, Zarić SD, Djukic J. Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution. in The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020. 2020;:161-161. https://hdl.handle.net/21.15107/rcub_cherry_6357 .
Milovanović, Milan R., Dherbassy, Quentin, Wencel-Delord, Joanna, Colobert, Françoise, Zarić, Snežana D., Djukic, Jean-Pierre, "Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution" in The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020 (2020):161-161, https://hdl.handle.net/21.15107/rcub_cherry_6357 .