title: A DFT study of permanganate oxidation of toluene and its ortho-nitroderivatives.
abstract: Calculations of alternative oxidation pathways of toluene and its ortho-substituted nitro derivatives by permanganate anion have been performed. The competition between methyl group and ring oxidation has been addressed. Acceptable results have been obtained using IEFPCM/B3LYP/6-31+G(d,p) calculations with zero-point (ZPC) and thermal corrections, as validated by comparison with the experimental data. It has been shown that ring oxidation reactions proceed via relatively early transition states that become quite unsymmetrical for reactions involving ortho-nitrosubstituted derivatives. Transition states for the hydrogen atom abstraction reactions, on the other hand, are late. All favored reactions are characterized by the Gibbs free energy of activation, ΔG(≠), of about 25 kcal mol(-1). Methyl group oxidations are exothermic by about 20 kcal mol(-1) while ring oxidations are around thermoneutrality.
authors: Institute of Applied Radiation Chemistry, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924, Lodz, Poland.
authors: Paweł
authors: P
authors: Adamczyk
authors: Reto S
authors: RS
authors: Wijker
authors: Thomas B
authors: TB
authors: Hofstetter
authors: Piotr
authors: P
authors: Paneth
mesh_terms: D000397:Air Pollution; D006859:Hydrogen / Q000737:chemistry; D007700:Kinetics; D017895:Manganese Compounds / Q000737:chemistry*; D017672:Nitrogen Compounds / Q000737:chemistry* / Q000633:toxicity; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry*; D013046:Specific Gravity; D013816:Thermodynamics; D014050:Toluene / Q000737:chemistry*
chemical_list: D017895:Manganese Compounds; D017672:Nitrogen Compounds; D010087:Oxides; C048856:permanganic acid; D014050:Toluene; D006859:Hydrogen