Accession Number : ADA182453

Title :   A Comparative Analyis of O-O Bond Properties in Dioxirane, Hydrogen Peroxide, and Peroxytrifluoroacetic Acid,

Corporate Author : NEW ORLEANS UNIV LA DEPT OF CHEMISTRY

Personal Author(s) : Politizer,Peter ; Bar-Adon,Ruth ; Miller,Richard S.

Report Date : 1987

Pagination or Media Count : 5

Abstract : An interesting point that is brought out by our analyses of hydrogen peroxide and peroxytrifluoroacetic acid is the rather limited sensitivity of the OOH group to the remainder of the molecule. The structural parameters, the OO bond deviation indices, and the bond orders of both the OO and OH bonds are essentially unchanged by either rotation around the OO bond in H2O2 or the substitution of the electron-withdrawing CF3C-(==O)-group. The latter factor does, however, significantly affect the electostatic potential; the negative regions associated with the peroxide oxygens become weaker, especially the one nearer to the substituent. Thus a substantial degree of polarity is introduced into the OO bond of peroxytrifluoroacetic acid. Our study has shown that the OO bond in dioxirane is qualitatively different from those in hydrogen peroxide and peroxytrifluoroacetic acid. In dioxirane this bond is considerabley strained, and consequently weaker than in these peroxides. The CO bonds are also weakened by strain. The highly reactive nature of dioxirane, and its ability to act as an oxygen atom transfer agent, are thus readily understandable.

Descriptors :   *HYDROGEN PEROXIDE, *OXYGEN, *CHEMICAL BONDS, *ACETIC ACID, *OXYGEN HETEROCYCLIC COMPOUNDS, MOLECULAR PROPERTIES, MOLECULAR ORBITALS, HYDROXYL RADICALS, ELECTROSTATICS, FLUORINE COMPOUNDS, MOLECULE MOLECULE INTERACTIONS, ATOMS, INDEXES, PEROXIDES, POLARITY, SENSITIVITY, STRUCTURAL PROPERTIES, TRANSFER

Subject Categories : Inorganic Chemistry
      Organic Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE