Issue 12, 2024

Study of heavy atom influence on poly-halogenated compounds using DP4/MM-DP4+/DP4+: insights and trends

Abstract

Nuclear magnetic resonance (NMR) spectroscopy complemented by density functional theory (DFT) calculations is a crucial tool for structural elucidation. Nevertheless, the precision of NMR predictions is influenced by the ‘heavy atom effect’, wherein heavy atoms affect the shielding values of neighboring light atoms (HALA effect). Standard practice in the field involves removing the conflicting signals. However, in the case of polyhalogenated molecules, this is challenging due to the significant amount of information that ends up being lost. In this study the HALA is thoroughly investigated in the context of three leading probability methods: DP4, MM-DP4+, and DP4+. The results show that DP4+ is more sensitive to C–Cl or C–Br signals, which is a consequence of the longer bond lengths computed with DFT. Removing conflicting signals is highly effective in DP4+, but has an uncertain outcome in methods based on molecular mechanics geometries, such as DP4 and MM-DP4+. A detailed investigation of the effect of bond distance on the corresponding chemical shifts has also been conducted.

Graphical abstract: Study of heavy atom influence on poly-halogenated compounds using DP4/MM-DP4+/DP4+: insights and trends

Supplementary files

Article information

Article type
Paper
Submitted
20 Dec 2023
Accepted
13 Feb 2024
First published
16 Feb 2024

Org. Biomol. Chem., 2024,22, 2435-2442

Study of heavy atom influence on poly-halogenated compounds using DP4/MM-DP4+/DP4+: insights and trends

L. Passaglia, M. M. Zanardi and A. M. Sarotti, Org. Biomol. Chem., 2024, 22, 2435 DOI: 10.1039/D3OB02077K

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