A theoretical study of the effects of polar substitution on the activation barriers for internal rotation around the C-N bond in p-substituted nitrosobenzenes: comparison of DFT and MP2 calculations

Authors

ŞAFAK ÖZHAN KOCAKAYA
NECMETTİN PİRİNÇÇİOĞLU

DOI

10.3906/kim-0909-272

Abstract

The activation barriers for internal rotation around the C-N bond in p-substituted nitrosobenzenes were calculated using the density functional theory (DFT) and second-order Møller-Plesset (MP2) methods with the 6-31+g(d) basis set. The polarisable continuum model (PCM) was used to model the solvent effect. An explicit water molecule was also introduced to form a hydrogen bond with the nitrosogroup and its effect on the barrier was studied by DFT. The barriers were well-correlated with Hammett sigma^+ rather than sigma values, meaning a strong resonance effect. The MP2 method produces better and comparable results with the few available experimental values.

Keywords

Para-substituted nitrosobenzenes, C-N bond rotation, polar substituent effect, molecular modelling DFT, MP2, PCM.

First Page

399

Last Page

410

Recommended Citation

KOCAKAYA, ŞAFAK ÖZHAN and PİRİNÇÇİOĞLU, NECMETTİN (2010) "A theoretical study of the effects of polar substitution on the activation barriers for internal rotation around the C-N bond in p-substituted nitrosobenzenes: comparison of DFT and MP2 calculations," Turkish Journal of Chemistry: Vol. 34: No. 3, Article 9. https://doi.org/10.3906/kim-0909-272
Available at: https://journals.tubitak.gov.tr/chem/vol34/iss3/9