Beilstein J. Org. Chem.2023,19, 89–90, doi:10.3762/bjoc.19.8
studied by single-crystal X-ray diffraction by Khrizanforov et al., and the preferred conformations were substantiated by DFT calculations [6].
Finally, Hersh and Chan presented a method to improve the accuracy of 31P NMR chemical shift calculations by use of scalingmethods [7].
György Keglevich
Budapest
Beilstein J. Org. Chem.2023,19, 36–56, doi:10.3762/bjoc.19.4
series of tri- and tetracoordinate phosphorus compounds using several basis sets and density functional theory (DFT) functionals gave a modest fit to experimental chemical shifts, but an excellent linear fit when plotted against the experimental values. The resultant scalingmethods were then applied to
/RMSD = 6.9/8.5 ppm and 6.8/9.1 ppm, respectively, over an experimental chemical shift range of −181 to 356 ppm. Due to the unexplained failures observed, we recommend use of more than one method when looking at novel structures.
Keywords: calculations; DFT; phosphorus NMR; scalingmethods
at a time.
In the same way that improved results are obtainable for both 1H and 13C NMR chemical shifts using scalingmethods, calculation of 31P NMR chemical shifts benefit as well from scaling. Chesnut first showed that scaling of the paramagnetic term of chemical shieldings calculated using the
PDF
Graphical Abstract
Figure 1:
Training set of tri- and tetracoordinate phosphorus compounds; chemical shifts are in ppm, referenc...