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

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.

DOI

10.3906/kim-0909-272

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, Ş. Ö, & PİRİNÇÇİOĞLU, N (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 34 (3): 399-410. https://doi.org/10.3906/kim-0909-272