Computational aspects of ¹⁹F NMR

Abstract

This review covers most recent advances in computation of 19F NMR chemical shifts and spin – spin coupling constants involving 19F nucleus calculated at different levels of theory. It deals mainly with electronic and stereochemical effects influencing these parameters, with a special emphasis on practical applications of such calculations. For 19F NMR chemical shifts, a good deal of attention is focused on less common solid state studies, in addition to much more popular liquid state data. For spin – spin coupling constants, the main interest is concentrated on the most popular 19F–1H, 19F–13C and 19F–19F couplings providing marked stereochemical behaviour. The bibliography includes 149 references. In memory of Professor Rubén Horacio Contreras, to commemorate his achievements in the field of theoretical and computational 19F NMR.

Computational 1H NMR: Part 1. Theoretical background

“…On the contrary, in the supermolecular solvation model approach applied for the calculation of chemical shifts and spin–spin coupling constants, solvent molecules are added directly into calculation space of the compound under study to form its solvation complexes in the IEF PCM medium. All this is discussed in much detail in the cited sources and, in part, in our recent review …”

“…Indeed, predicting ZPVC is an important step in the accurate evaluation of such molecular properties as 1 H NMR chemical shifts and 1 H– 1 H spin–spin coupling constants. Further theoretical details dealing with the vibrational corrections to NMR parameters are given in the fundamental monograph on molecular electromagnetism by Sauer and, in part, in our previous review …”

“…Theoretical aspects of the calculation of two basic nuclear magnetic resonance parameters, chemical shifts and spin–spin coupling constants, are well covered in a fundamental handbook of molecular electromagnetism by Stephan Sauer and in a number of related reviews on theoretical and computational aspects of NMR together with those previous reviews treating NMR parameters on relativistic grounds (I apologize to the authors of numerous related reviews, which are not cited above). Present review deals with the computation of 1 H NMR chemical shifts and 1 H– 1 H spin–spin coupling constants and is written in continuation of the four previous reviews published in Progress in NMR Spectroscopy very recently in the interim of 2017–2019.…”

Recent advances in computational 31P NMR: Part 1. Chemical shifts

“…Theoretical aspects of the calculation of nuclear magnetic resonance (NMR) parameters are thoroughly reviewed in a fundamental handbook of molecular electromagnetism by Stephan Sauer and in a number of related reviews on theoretical and computational aspects of NMR parameters, together with those evaluated on relativistic level . The present review covers computational aspects of 31 P NMR and is written in continuation of our four recent reviews published in Progress in NMR Spectroscopy and three reviews that appeared in Magnetic Resonance in Chemistry very recently dealing with computation of 1 H, 13 C, and 15 N NMR chemical shifts and spin–spin coupling constants involving those nuclei.…”

Recent advances in computational 31P NMR: Part 2. Spin–spin coupling constants

“…Calculation of nuclear magnetic resonance (NMR) parameters in a wide variety of chemical compounds and biochemical species has become very popular in the past 10–15 years, providing a breakthrough into theoretical and stereochemical aspects of chemical structure . In particular, calculation of 31 P NMR chemical shifts and heteronuclear spin–spin coupling constants, involving phosphorous in a wide series of different organophosphorus compounds and phosphorus‐containing complexes and clusters together with different bioorganic phosphorus compounds like phosphorus containing nucleosides and nucleotides, natural and synthetic peptides, DNA, and RNA, is of utmost importance in view of the structural information that could be gained from these calculations.…”