Journalartikel

Jahr der Veröffentlichung: 2021

Seiten: 20837-20848

Zeitschrift: Journal of the American Chemical Society

Bandnummer: 143

Heftnummer: 49

ISSN: 0002-7863

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

Verlag: 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-Zitierstil: 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-Zitierstil: 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