Naslov
Prereactive complexes in chlorination of benzene, triazine, and tetrazine. A quantum chemical study

Autori
Šakić, Davor ; Vrček, Valerije

Izvornik
Journal of physical chemistry. A (1089-5639) 116 (2012), 4; 1298-1306

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
aromatic substitution; stochastic search; chlorine; DFT; MP2

Sažetak
In order to perform a complete search for prereactive complexes between arenes (benzene and triazine) and chlorine, stochastic search method was employed. All stationary points were optimized at B3LYP, M05-2X, and MP2 levels, while improved energetics have been calculated using B2PLYP-D method which includes van der Waals corrections important for accurate description of dispersion forces. Several new intermediates, not reported earlier, have been located and their mechanistic relevance has been discussed. It is suggested that in the case of chlorination of benzene the T-shaped complex precedes the formation of classical pi-complex. No Wheland sigma-complex has been found on the corresponding energy surface, unless explicit counterions (BF4- or AlCl4-) are included in calculations. Neither pi- nor sigma-complexes were located on the reactant side of chlorination of triazine, but only linear and T-shaped complexes are identified as stable minima. These structures are proposed as important prereactive complexes on the reaction coordinate for chlorination of triazine.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA