Wednesday, November 16, 2016

Calculation of NMR Spin–Spin Coupling Constants in Strychnine

Helgaker, T.; Jaszuński, M.; Świder, P. J. Org. Chem. 2016
Contributed by Steven Bachrach
Reposted from Computational Organic Chemistry with permission

Helgaker, Jaszunski, and Swider1 have examined the use of B3LYP with four different basis sets to compute the spin-spin coupling constants in strychnine 1.

1
They used previously optimized coordinates of the two major conformations of strychnine, shown in Figure 1.

Conformer A

Conformer B
Figure 1. Confrmations of strychnine 1.

They tested four basis sets designed for NMR computations: pcJ-0,2 pcJ-1,2 6-31G-J,3 and 6-311G-J.3 pCJ-0 and 6-31G-J are relatively small basis sets, while the other two are considerably larger.

All four basis sets provide values of the 122 J(C-H) with a root mean square deviation of less than 0.6 Hz. J(HH) and J(CC) coupling constants are also well predicted, especially with the larger pcJ-1 basis set. They also examined the four Ramsey terms in the coupling model. The Fermi contact term dominates, and if the large pcJ-1 basis set is used to calculate it, and the smaller pcJ-0 basis set is used for the other three terms, the RMS error only increases from 0.18 to 0.20 Hz. Taking this to the extreme, they omitted calculating any of the non-Fermi contact terms, with again only small increases in the RMS – even with the small pcJ-0 basis set. Considering the computational costs, one should seriously consider whether the non-Fermi contact terms and a small basis set might be satisfactory for your own problem(s) at hand.

References

1) Helgaker, T.; Jaszuński, M.; Świder, P., "Calculation of NMR Spin–Spin Coupling Constants in Strychnine." J. Org. Chem. 2016, ASAP, DOI: 10.1021/acs.joc.6b02157.
2) Jensen, F., "The Basis Set Convergence of Spin−Spin Coupling Constants Calculated by Density Functional Methods." J. Chem. Theor. Comput. 2006, 2, 1360-1369, DOI: 10.1021/ct600166u.
3) Kjær, H.; Sauer, S. P. A., "Pople Style Basis Sets for the Calculation of NMR Spin–Spin Coupling Constants: the 6-31G-J and 6-311G-J Basis Sets." J. Chem. Theor. Comput. 2011, 7, 4070-4076, DOI: 10.1021/ct200546q.

InChIs

Strychnine 1: InChI=1S/C21H22N2O2/c24-18-10-16-19-13-9-17-21(6-7-22(17)11-12(13)5-8-25-16)14-3-1-2-4-15(14)23(18)20(19)21/h1-5,13,16-17,19-20H,6-11H2/t13-,16-,17-,19-,20-,21+/m0/s1
InChIKey=QMGVPVSNSZLJIA-FVWCLLPLSA-N

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