Predicting Pt-195 NMR Chemical Shift and 1J(195Pt-31P) Coupling Constant for Pt(0) Complexes Using the NMR-DKH Basis Sets

Pt(0) complexes have been widely used as catalysts for important reactions, such as the hydrosilylation of olefins. In this context, nuclear magnetic resonance (NMR) spectroscopy plays an important role in characterising of new structures and elucidating reaction mechanisms. In particular, the Pt-19...

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Autores principales:	Joyce H. C. e Silva, Hélio F. Dos Santos, Diego F. S. Paschoal
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	Pt(0) complexes catalysis NMR Pt-195 chemical shift basis set DFT Chemistry QD1-999
Acceso en línea:	https://doaj.org/article/df439ef04f8f4324811360b6522c9bba
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spelling	oai:doaj.org-article:df439ef04f8f4324811360b6522c9bba2021-11-25T18:12:32ZPredicting Pt-195 NMR Chemical Shift and <sup>1</sup>J(<sup>195</sup>Pt-<sup>31</sup>P) Coupling Constant for Pt(0) Complexes Using the NMR-DKH Basis Sets10.3390/magnetochemistry71101482312-7481https://doaj.org/article/df439ef04f8f4324811360b6522c9bba2021-11-01T00:00:00Zhttps://www.mdpi.com/2312-7481/7/11/148https://doaj.org/toc/2312-7481Pt(0) complexes have been widely used as catalysts for important reactions, such as the hydrosilylation of olefins. In this context, nuclear magnetic resonance (NMR) spectroscopy plays an important role in characterising of new structures and elucidating reaction mechanisms. In particular, the Pt-195 NMR is fundamental, as it is very sensitive to the ligand type and the oxidation state of the metal. In the present study, quantum mechanics computational schemes are proposed for the theoretical prediction of the Pt-195 NMR chemical shift and <sup>1</sup>J(<sup>195</sup>Pt–<sup>31</sup>P) in Pt(0) complexes. The protocols were constructed using the B3LYP/LANL2DZ/def2-SVP/IEF-PCM(UFF) level for geometry optimization and the GIAO-PBE/NMR-DKH/IEF-PCM(UFF) level for NMR calculation. The NMR fundamental quantities were then scaled by empirical procedures using linear correlations. For a set of 30 Pt(0) complexes, the results showed a mean absolute deviation (MAD) and mean relative deviation (MRD) of only 107 ppm and 2.3%, respectively, for the Pt-195 NMR chemical shift. When the coupling constant is taken into account, the MAD and MRD for a set of 33 coupling constants in 26 Pt(0) complexes were of 127 Hz and 3.3%, respectively. In addition, the models were validated for a group of 17 Pt(0) complexes not included in the original group that had MAD/MRD of 92 ppm/1.7% for the Pt-195 NMR chemical shift and 146 Hz/3.6% for the <sup>1</sup>J(<sup>195</sup>Pt–<sup>31</sup>P).Joyce H. C. e SilvaHélio F. Dos SantosDiego F. S. PaschoalMDPI AGarticlePt(0) complexescatalysisNMRPt-195 chemical shiftbasis setDFTChemistryQD1-999ENMagnetochemistry, Vol 7, Iss 148, p 148 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Pt(0) complexes catalysis NMR Pt-195 chemical shift basis set DFT Chemistry QD1-999
spellingShingle	Pt(0) complexes catalysis NMR Pt-195 chemical shift basis set DFT Chemistry QD1-999 Joyce H. C. e Silva Hélio F. Dos Santos Diego F. S. Paschoal Predicting Pt-195 NMR Chemical Shift and <sup>1</sup>J(<sup>195</sup>Pt-<sup>31</sup>P) Coupling Constant for Pt(0) Complexes Using the NMR-DKH Basis Sets
description	Pt(0) complexes have been widely used as catalysts for important reactions, such as the hydrosilylation of olefins. In this context, nuclear magnetic resonance (NMR) spectroscopy plays an important role in characterising of new structures and elucidating reaction mechanisms. In particular, the Pt-195 NMR is fundamental, as it is very sensitive to the ligand type and the oxidation state of the metal. In the present study, quantum mechanics computational schemes are proposed for the theoretical prediction of the Pt-195 NMR chemical shift and <sup>1</sup>J(<sup>195</sup>Pt–<sup>31</sup>P) in Pt(0) complexes. The protocols were constructed using the B3LYP/LANL2DZ/def2-SVP/IEF-PCM(UFF) level for geometry optimization and the GIAO-PBE/NMR-DKH/IEF-PCM(UFF) level for NMR calculation. The NMR fundamental quantities were then scaled by empirical procedures using linear correlations. For a set of 30 Pt(0) complexes, the results showed a mean absolute deviation (MAD) and mean relative deviation (MRD) of only 107 ppm and 2.3%, respectively, for the Pt-195 NMR chemical shift. When the coupling constant is taken into account, the MAD and MRD for a set of 33 coupling constants in 26 Pt(0) complexes were of 127 Hz and 3.3%, respectively. In addition, the models were validated for a group of 17 Pt(0) complexes not included in the original group that had MAD/MRD of 92 ppm/1.7% for the Pt-195 NMR chemical shift and 146 Hz/3.6% for the <sup>1</sup>J(<sup>195</sup>Pt–<sup>31</sup>P).
format	article
author	Joyce H. C. e Silva Hélio F. Dos Santos Diego F. S. Paschoal
author_facet	Joyce H. C. e Silva Hélio F. Dos Santos Diego F. S. Paschoal
author_sort	Joyce H. C. e Silva
title	Predicting Pt-195 NMR Chemical Shift and <sup>1</sup>J(<sup>195</sup>Pt-<sup>31</sup>P) Coupling Constant for Pt(0) Complexes Using the NMR-DKH Basis Sets
title_short	Predicting Pt-195 NMR Chemical Shift and <sup>1</sup>J(<sup>195</sup>Pt-<sup>31</sup>P) Coupling Constant for Pt(0) Complexes Using the NMR-DKH Basis Sets
title_full	Predicting Pt-195 NMR Chemical Shift and <sup>1</sup>J(<sup>195</sup>Pt-<sup>31</sup>P) Coupling Constant for Pt(0) Complexes Using the NMR-DKH Basis Sets
title_fullStr	Predicting Pt-195 NMR Chemical Shift and <sup>1</sup>J(<sup>195</sup>Pt-<sup>31</sup>P) Coupling Constant for Pt(0) Complexes Using the NMR-DKH Basis Sets
title_full_unstemmed	Predicting Pt-195 NMR Chemical Shift and <sup>1</sup>J(<sup>195</sup>Pt-<sup>31</sup>P) Coupling Constant for Pt(0) Complexes Using the NMR-DKH Basis Sets
title_sort	predicting pt-195 nmr chemical shift and <sup>1</sup>j(<sup>195</sup>pt-<sup>31</sup>p) coupling constant for pt(0) complexes using the nmr-dkh basis sets
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/df439ef04f8f4324811360b6522c9bba
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Predicting Pt-195 NMR Chemical Shift and <sup>1</sup>J(<sup>195</sup>Pt-<sup>31</sup>P) Coupling Constant for Pt(0) Complexes Using the NMR-DKH Basis Sets

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