ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

  A frontier orbital analysis of the oxidation of alkenes by thallium(III) salts

M. Strašák and J. Majer

Department of Analytical Chemistry, Faculty of Pharmacy, Komenský University, 880 34 Bratislava

Abstract: Application of the perturbation MO treatment based on frontier orbitals (FO's) was utilized in the interpretation of the Taft correlation in the oxidn. of alkenes by Th(III) salts. There is a good linear relationship between the logarithm of the reaction rate k and the inverse of the FMO gap. In order to elucidate the mechanistic similarities obsd. between the oxymetallation reactions and some other electrophilic addns. to olefinic systems, comparative FMO anal. has been made and implications of these results to the reactivity-selectivity principle (RSP) are discussed. The model suggests that it is the differential HOMO-LUMO gap for a given substrate and reacting electrophiles that governs substrate selectivity.

Full paper in Portable Document Format: 356a797.pdf

Chemical Papers 35 (6) 797–807 (1981)