Formation of Dioxirane from Carbonyl Oxide

Abstract

The isomerization (a) should be exothermic and should have an activation barrier of 23 kcal mol−1. This follows from the results of ab initio calculations, which, moreover, suggest an initiating pyramidalization at the central O atom, which is facilitated by π‐donor substituents like fluorine: In cis‐ and trans‐HFCO2 the activation energy is still only 17 and 8 kcal mol−1, respectively. However, fluorodixirane is kinetically less stable than 2. Only geminal methyl groups effect both a thermodynamic and a kinetic stabilization. (Figure Presented.) Copyright © 1988 by VCH Verlagsgesellschaft mbH, Germany