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 journalJournal article

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 journalJournal article

Harvard

Lacerda Jr., EG, Kamounah, FS, Coutinho, K, Sauer, SPA, Hansen, PE & Hammerich, O 2019, 'Computational prediction of the 1H and 13C NMR chemical shifts for protonated alkylpyrroles: electron correlation and not solvation is the salvation', ChemPhysChem, vol. 20, no. 1, pp. 78-91. https://doi.org/10.1002/cphc.201801066

APA

Lacerda Jr., E. G., Kamounah, F. S., Coutinho, K., Sauer, S. P. A., Hansen, P. E., & Hammerich, O. (2019). Computational prediction of the 1H and 13C NMR chemical shifts for protonated alkylpyrroles: electron correlation and not solvation is the salvation. ChemPhysChem, 20(1), 78-91. https://doi.org/10.1002/cphc.201801066

Vancouver

Lacerda Jr. EG, Kamounah FS, Coutinho K, Sauer SPA, Hansen PE, Hammerich O. Computational prediction of the 1H and 13C NMR chemical shifts for protonated alkylpyrroles: electron correlation and not solvation is the salvation. ChemPhysChem. 2019;20(1):78-91. https://doi.org/10.1002/cphc.201801066

Author

Lacerda Jr., Evanildo Gomes ; Kamounah, Fadhil S ; Coutinho, Kaline ; Sauer, Stephan P. A. ; Hansen, Poul Erik ; Hammerich, Ole. / Computational prediction of the 1H and 13C NMR chemical shifts for protonated alkylpyrroles : electron correlation and not solvation is the salvation. In: ChemPhysChem. 2019 ; Vol. 20, No. 1. pp. 78-91.

Bibtex

@article{f39ab3c24cd348c68957cfbe6e052298,
title = "Computational prediction of the 1H and 13C NMR chemical shifts for protonated alkylpyrroles: electron correlation and not solvation is the salvation",
abstract = "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, M{\o}ller-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.",
keywords = "Faculty of Science, MP2, B3LYP, Solvent effects, density functional theory (DFT), NMR, chemical shift, protonated alkylpyrroles",
author = "{Lacerda Jr.}, {Evanildo Gomes} and Kamounah, {Fadhil S} and Kaline Coutinho and Sauer, {Stephan P. A.} and Hansen, {Poul Erik} and Ole Hammerich",
year = "2019",
doi = "10.1002/cphc.201801066",
language = "English",
volume = "20",
pages = "78--91",
journal = "ChemPhysChem",
issn = "1439-4235",
publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",
number = "1",

}

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