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The Affinity of Some Lewis Bases for Hexafluoroisopropanol as a Reference Lewis Acid: An ITC/DFT Study

Authorized Users Only
2020
Authors
Milovanović, Milan R.
Dherbassy, Quentin
Wencel‐Delord, Joanna
Colobert, Françoise
Zarić, Snežana D.
Đukić, Jean-Pierre
Article (Published version)
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Abstract
To figure out the possible role of 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) as well as to provide reference thermochemical data in solution, the formation of Lewis acid-base complexes between HFIP (Lewis acid) and a series of 8 different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) was examined by isothermal titration calorimetry (ITC) experiments and static density functional theory augmented with Dispersion (DFT−D) calculations. Measured ITC association enthalpy values (ΔHa) lie between −9.3 and −14 kcal mol−1. Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems compared to the ITC data with ΔHa values ranging from −8.5 to −12.7 kcal mol−1. 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 HFIP-base complexation: its main effect is t...o 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 microstructuring of the medium but also more explicitly by affecting bonds’ polarization at the Lewis bases.

Keywords:
density functional theory / hexafluoroisopropanol / isothemal titration calorimetry / Lewis adducts / solvation
Source:
ChemPhysChem, 2020, 21, 18, 2136-2142
Publisher:
  • Wiley
Projects:
  • Noncovalent interactions of pi-systems and their role in molecular recognition (RS-172065)
  • ANR-DFG project COCOORDCHEM.
  • Campus France and the Fund for young talents – Dositeja.
Note:
  • Peer-reviewed manuscript: https://cherry.chem.bg.ac.rs/handle/123456789/4339

DOI: 10.1002/cphc.202000560

ISSN: 1439-7641

WoS: 000559834100001

Scopus: 2-s2.0-85089504324
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2
URI
http://cherry.chem.bg.ac.rs/handle/123456789/4337
Collections
  • Publikacije
  • Publikacije
Institution
Hemijski fakultet
TY  - JOUR
AU  - Milovanović, Milan R.
AU  - Dherbassy, Quentin
AU  - Wencel‐Delord, Joanna
AU  - Colobert, Françoise
AU  - Zarić, Snežana D.
AU  - Đukić, Jean-Pierre
PY  - 2020
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/4337
AB  - To figure out the possible role of 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) as well as to provide reference thermochemical data in solution, the formation of Lewis acid-base complexes between HFIP (Lewis acid) and a series of 8 different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) was examined by isothermal titration calorimetry (ITC) experiments and static density functional theory augmented with Dispersion (DFT−D) calculations. Measured ITC association enthalpy values (ΔHa) lie between −9.3 and −14 kcal mol−1. Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems compared to the ITC data with ΔHa values ranging from −8.5 to −12.7 kcal mol−1. 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 HFIP-base complexation: its 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 microstructuring of the medium but also more explicitly by affecting bonds’ polarization at the Lewis bases.
PB  - Wiley
T2  - ChemPhysChem
T1  - The Affinity of Some Lewis Bases for Hexafluoroisopropanol as a Reference Lewis Acid: An ITC/DFT Study
VL  - 21
IS  - 18
SP  - 2136
EP  - 2142
DO  - 10.1002/cphc.202000560
ER  - 
@article{
author = "Milovanović, Milan R. and Dherbassy, Quentin and Wencel‐Delord, Joanna and Colobert, Françoise and Zarić, Snežana D. and Đukić, Jean-Pierre",
year = "2020",
url = "http://cherry.chem.bg.ac.rs/handle/123456789/4337",
abstract = "To figure out the possible role of 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) as well as to provide reference thermochemical data in solution, the formation of Lewis acid-base complexes between HFIP (Lewis acid) and a series of 8 different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) was examined by isothermal titration calorimetry (ITC) experiments and static density functional theory augmented with Dispersion (DFT−D) calculations. Measured ITC association enthalpy values (ΔHa) lie between −9.3 and −14 kcal mol−1. Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems compared to the ITC data with ΔHa values ranging from −8.5 to −12.7 kcal mol−1. 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 HFIP-base complexation: its 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 microstructuring of the medium but also more explicitly by affecting bonds’ polarization at the Lewis bases.",
publisher = "Wiley",
journal = "ChemPhysChem",
title = "The Affinity of Some Lewis Bases for Hexafluoroisopropanol as a Reference Lewis Acid: An ITC/DFT Study",
volume = "21",
number = "18",
pages = "2136-2142",
doi = "10.1002/cphc.202000560"
}
Milovanović MR, Dherbassy Q, Wencel‐Delord J, Colobert F, Zarić SD, Đukić J. The Affinity of Some Lewis Bases for Hexafluoroisopropanol as a Reference Lewis Acid: An ITC/DFT Study. ChemPhysChem. 2020;21(18):2136-2142
Milovanović, M. R., Dherbassy, Q., Wencel‐Delord, J., Colobert, F., Zarić, S. D.,& Đukić, J. (2020). The Affinity of Some Lewis Bases for Hexafluoroisopropanol as a Reference Lewis Acid: An ITC/DFT Study.
ChemPhysChemWiley., 21(18), 2136-2142.
https://doi.org/10.1002/cphc.202000560
Milovanović Milan R., Dherbassy Quentin, Wencel‐Delord Joanna, Colobert Françoise, Zarić Snežana D., Đukić Jean-Pierre, "The Affinity of Some Lewis Bases for Hexafluoroisopropanol as a Reference Lewis Acid: An ITC/DFT Study" 21, no. 18 (2020):2136-2142,
https://doi.org/10.1002/cphc.202000560 .

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