Journal article

Publication year: 2021

Pages: 20837-20848

Journal: Journal of the American Chemical Society

Volume number: 143

Issue number: 49

ISSN: 0002-7863

DOI Link: https://doi.org/10.1021/jacs.1c09222

Publisher: American Chemical Society

Abstract: 
We suggest a scale of dispersion energy donors (DEDs) that allows for direct comparisons with steric effects. This scale is based on the classic A-values and allows groups to reorient to minimize strain, thereby providing an advantage over raw group polarizabilities. The A-value can no longer be considered purely a steric factor. Even for groups that do not participate in charge transfer or electrostatic interactions, the A-value includes Pauli repulsion (steric hindrance) and attractive London dispersion (LD) interactions. Although the common assumption is that, at the distances found in monosubstituted cyclohexanes, steric demands are the key factors influencing conformer preferences, we show in this computational study that there is a non-negligible LD part. We use this system to build a DED scale and a complementary steric scale. These scales are quantitatively comparable, as they are based on the same system, and allow for comparison of the two competing interactions in experimentally relevant settings. In addition, we show that LD interactions can be used to explain puzzling data regarding relative group sizes.

Harvard Citation style: Solel, E., Ruth, M. and Schreiner, P. (2021) London Dispersion Helps Refine Steric A-Values: Dispersion Energy Donor Scales, Journal of the American Chemical Society, 143(49), pp. 20837-20848. https://doi.org/10.1021/jacs.1c09222

APA Citation style: Solel, E., Ruth, M., & Schreiner, P. (2021). London Dispersion Helps Refine Steric A-Values: Dispersion Energy Donor Scales. Journal of the American Chemical Society. 143(49), 20837-20848. https://doi.org/10.1021/jacs.1c09222