Density functional theory study of (13)C NMR chemical shift of chlorinated compounds

Magnetic Resonance in Chemistry : MRC
Songqing LiZhiqiang Zhou

Abstract

The use of the standard density functional theory (DFT) leads to an overestimation of the paramagnetic contribution and underestimation of the shielding constants, especially for chlorinated carbon nuclei. For that reason, the predictions of chlorinated compounds often yield too high chemical shift values. In this study, the WC04 functional is shown to be capable of reducing the overestimation of the chemical shift of Cl-bonded carbons in standard DFT functionals and to show a good performance in the prediction of (13)C NMR chemical shifts of chlorinated organic compounds. The capability is attributed to the minimization of the contributions that intensively increase the chemical shift in the WC04. Extensive computations and analyses were performed to search for the optimal procedure for WC04. The B3LYP and mPW1PW91 standard functionals were also used to evaluate the performance. Through detailed comparisons between the basis set effects and the solvent effects on the results, the gas-phase GIAO/WC04/6-311+G(2d,p)//B3LYP/6-31+G(d,p) was found to be specifically suitable for the prediction of (13)C NMR chemical shifts of chlorides in both chlorinated and non-chlorinated carbons. Further tests with eight molecules in the probe se...Continue Reading

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Citations

May 16, 2013·Magnetic Resonance in Chemistry : MRC·Gary E MartinR Thomas Williamson
Nov 23, 2012·Magnetic Resonance in Chemistry : MRC·Ran-Ran SunNai-Yun Ji
Jul 25, 2019·Magnetic Resonance in Chemistry : MRC·Ibon AlkortaAlain Fruchier
May 9, 2013·Organic Letters·Nai-Yun JiMing-Feng Qiao
Jul 25, 2012·Organic Letters·Feng-Ping MiaoNai-Yun Ji

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