Computational prediction of the 1H and 13C NMR chemical shifts for protonated alkylpyrroles: electron correlation and not solvation is the salvation
Research output: Contribution to journal › Journal article › Research › peer-review
Standard
Computational prediction of the 1H and 13C NMR chemical shifts for protonated alkylpyrroles : electron correlation and not solvation is the salvation. / Lacerda Jr., Evanildo Gomes; Kamounah, Fadhil S; Coutinho, Kaline; Sauer, Stephan P. A.; Hansen, Poul Erik; Hammerich, Ole.
In: ChemPhysChem, Vol. 20, No. 1, 2019, p. 78-91.Research output: Contribution to journal › Journal article › Research › peer-review
Harvard
APA
Vancouver
Author
Bibtex
}
RIS
TY - JOUR
T1 - Computational prediction of the 1H and 13C NMR chemical shifts for protonated alkylpyrroles
T2 - electron correlation and not solvation is the salvation
AU - Lacerda Jr., Evanildo Gomes
AU - Kamounah, Fadhil S
AU - Coutinho, Kaline
AU - Sauer, Stephan P. A.
AU - Hansen, Poul Erik
AU - Hammerich, Ole
PY - 2019
Y1 - 2019
N2 - Prediction of chemical shifts in organic cations is known to be a challenge. In this article we meet this challenge for α-protonated alkylpyrroles, a class of compounds not yet studied in this context, and present a combined experimental and theoretical study of the 13C and 1H chemical shifts in three selected pyrroles. We have investigated the importance of the solvation model, basis set and quantum chemical method with the goal of developing a simple computational protocol, which allows prediction of 13C and 1H chemical shifts with a sufficient accuracy for identification of such compounds in mixtures. We find that density functional theory with the B3LYP functional is not sufficient for reproducing all 13C chemical shifts, while already the simplest correlated wave function model, Møller-Plesset perturbation theory (MP2), leads to almost perfect agreement with the experimental data. Treatment of solvent effects generally improves somewhat the agreement with experiment and can in most cases be accomplished by a simple polarizable continuum model. The only exception is the N-H proton, which requires inclusion of explicit solvent molecules in the calculation.
AB - Prediction of chemical shifts in organic cations is known to be a challenge. In this article we meet this challenge for α-protonated alkylpyrroles, a class of compounds not yet studied in this context, and present a combined experimental and theoretical study of the 13C and 1H chemical shifts in three selected pyrroles. We have investigated the importance of the solvation model, basis set and quantum chemical method with the goal of developing a simple computational protocol, which allows prediction of 13C and 1H chemical shifts with a sufficient accuracy for identification of such compounds in mixtures. We find that density functional theory with the B3LYP functional is not sufficient for reproducing all 13C chemical shifts, while already the simplest correlated wave function model, Møller-Plesset perturbation theory (MP2), leads to almost perfect agreement with the experimental data. Treatment of solvent effects generally improves somewhat the agreement with experiment and can in most cases be accomplished by a simple polarizable continuum model. The only exception is the N-H proton, which requires inclusion of explicit solvent molecules in the calculation.
KW - Faculty of Science
KW - MP2
KW - B3LYP
KW - Solvent effects
KW - density functional theory (DFT)
KW - NMR
KW - chemical shift
KW - protonated alkylpyrroles
U2 - 10.1002/cphc.201801066
DO - 10.1002/cphc.201801066
M3 - Journal article
C2 - 30452112
VL - 20
SP - 78
EP - 91
JO - ChemPhysChem
JF - ChemPhysChem
SN - 1439-4235
IS - 1
ER -
ID: 209054888