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

Abstract

This is the first part of two closely related reviews dealing with the computation of phosphorus-31 nuclear magnetic resonance chemical shifts in a wide series of organophosphorus compounds including complexes, clusters, and bioorganic phosphorus compounds. In particular, the analysis of the accuracy factors, such as substitution effects, solvent effects, vibrational corrections, and relativistic effects, is presented. This review is dedicated to the Full Member of the Russian Academy of Sciences Professor Boris A. Trofimov in view of his invaluable contribution to the field of synthesis, nuclear magnetic resonance, and computation studies of organophosphorus compounds. KEYWORDS computational P-31 NMR, P-31 chemical shiftsThis review is dedicated to the Full Member of the Russian Academy of Sciences Professor Boris A. Trofimov in view of his invaluable contribution to the field of synthesis, NMR investigation, and computational studies of organophosphorus compounds. He is the author of 43 books and chapters in books, some 70 reviews, about 1,500 research papers and has been a scientific supervisor for approximately 90 Ph.D. and 30 D.Sc. dissertations. The apogee of his creativity and scientific achievements is a fundamental book "The Chemistry

Computational 1H NMR: Part 1. Theoretical background

“…All this is discussed in much detail in the cited sources and, in part, in our recent review. [24] As an example of the latter, shown in Figure 6 are the intermolecular complexes of several pyrazines with one molecule of dimethyl sulfoxide in the IEF-PCM medium 23-30 studied by Semenov et al [108] (for details, see original publication). Another illustrative example is the intermolecular cluster of five molecules of nitrometane 31 studied by the same authors, [109] which is widely used for NMR referencing.…”

“…Further theoretical details dealing with the vibrational corrections to NMR parameters are given in the fundamental monograph on molecular electromagnetism by Sauer [1] and, in part, in our previous review. [24] The influence of the vibrational corrections to the values of isotropic shielding constants of hydrogen in 1 H NMR spectra calculated at the CCSD(T) level with different basis sets is exemplified in Figures 8 and 9 taken from a milestone publication in this field by Faber et al [115] Note. Adopted from Provasi, Aucar, and Sauer.…”

“…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 [1] and in a number of related reviews on theoretical and computational aspects of NMR [2][3][4][5][6][7][8][9][10][11][12][13][14][15] together with those previous reviews [16][17][18][19][20] 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 [21][22][23][24] published in Progress in NMR Spectroscopy very recently in the interim of 2017-2019.…”

Experimentally Established Benchmark Calculations of 31P NMR Quantities

“…The conformation [10] of phosphorous containing molecules, noncovalent interactions [11] and dynamic processes [12] involved in, can be elucidated by NMR. Quantum mechanical simulations of 31 P NMR quantities in such systems do not necessarily require specific soft‐ or hardware; this opening up new possibilities for advanced studies [13] . However, their application is limited due to the following reason.…”

“…Quantum mechanical simulations of 31 P NMR quantities in such systems do not necessarily require specific soft-or hardware; this opening up new possibilities for advanced studies. [13] However, their application is limited due to the following reason. One of the main spectral characteristics of NMR is the absolute chemical shielding, σ.…”