Analysis of the reactivities of organic compounds in hydrogen atom abstraction from their C-H bonds by the sulfate radical anion SO4

• Published in: Kinetics and catalysis 2008-03, Vol.49 (2), p.202-211
• Main Authors: Khursan, S. L., Semes’ko, D. G., Teregulova, A. N., Safiullin, R. L.
• Format: Article
• Language: English
• Subjects: Catalysis; Chemistry; Chemistry and Materials Science; Physical Chemistry
• ISSN: 0023-1584; 1608-3210
• DOI: 10.1134/S0023158408020067

An experimental rate constant data array (>50 values) for the reactions of the sulfate radical anion with the C-H bonds of various organic compounds is analyzed by Denisov’s intersecting parabolas method. The data array is divided into the following four groups according to the type of the C-H bond attacked and the br e value: compounds with primary C-H bonds ( br e = 13.14 ± 0.17), compounds with secondary C-H bonds remote from the polar groups ( br e = 12.64 ± 0.34), compounds with secondary α-C-H bonds ( br e = 13.28 ± 0.24), and compounds with tertiary C-H bonds. It is demonstrated by DFT calculations that the rate constant of the reaction SO 4 ·− + RH is determined by nonspecific solvation and by the ion-dipole interaction in the transition state of the reaction.