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Open AccessArticle

Relativistic Effects on NMR Parameters of Halogen-Bonded Complexes

1
Instituto de Química Médica, IQM-CSIC. Juan de la Cierva, 3, 28006 Madrid, Spain
2
Departamento de Química, Módulo 13, Facultad de Ciencias and Institute of Advanced Chemical Sciences (IadChem), Universidad Autónoma de Madrid, Campus de Excelencia UAM-CSIC, Cantoblanco, 28049 Madrid, Spain
*
Authors to whom correspondence should be addressed.
Academic Editor: Paulo Jorge Costa
Molecules 2019, 24(23), 4399; https://doi.org/10.3390/molecules24234399
Received: 13 November 2019 / Revised: 25 November 2019 / Accepted: 27 November 2019 / Published: 2 December 2019
(This article belongs to the Special Issue Halogen Bonding: Insights from Computational Tools)
Relativistic effects are found to be important for the estimation of NMR parameters in halogen-bonded complexes, mainly when they involve the heavier elements, iodine and astatine. A detailed study of 60 binary complexes formed between dihalogen molecules (XY with X, Y = F, Cl, Br, I and At) and four Lewis bases (NH3, H2O, PH3 and SH2) was carried out at the MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP computational level to show the extent of these effects. The NMR parameters (shielding and nuclear quadrupolar coupling constants) were computed using the relativistic Hamiltonian ZORA and compared to the values obtained with a non-relativistic Hamiltonian. The results show a mixture of the importance of the relativistic corrections as both the size of the halogen atom and the proximity of this atom to the basic site of the Lewis base increase. View Full-Text
Keywords: halogen bonding; astatine; relativistic effects; NMR; absolute shieldings; nuclear quadrupolar coupling constants halogen bonding; astatine; relativistic effects; NMR; absolute shieldings; nuclear quadrupolar coupling constants
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MDPI and ACS Style

Alkorta, I.; Elguero, J.; Yáñez, M.; Mó, O.; Montero-Campillo, M.M. Relativistic Effects on NMR Parameters of Halogen-Bonded Complexes. Molecules 2019, 24, 4399.

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