Organic Peroxide - Properties

Properties

The O-O bond distance in peroxides is about 1.45 A and the R-O-O angles (R = H, C) are about 110° (water-like). Characteristically, the C-O-O-R (R = H, C) dihedral angles are about 120°. The O-O bond is relatively weak, with a bond dissociation energy of 45 - 50 kcal/mol, less than half the strengths of C-C, C-H, and C-O bonds.

The oxidizing tendency of peroxides is related to the electronegativity of the substituents. Electrophilic peroxides are stronger O-atom transfer agents. For hydroperoxides, the O-atom donor tendency correlates with the acidity of the O-H bond. Thus, the order of oxidizing power is CF3CO3H > CH3CO3H > H2O2.

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