Abstract
Chemical oxidation of (TMP)MnIII(Cl) (TMP = the tetramesitylporphyrinato dianion) by Fe(ClO4)3 leads to the porphyrin-oxidized product (TMP·+)MnIII(ClO4)2. Magnetic measurements and EPR spectroscopy show that the total spin of the complex changes from S = 5/2 at high temperature to S = 3/2 at low temperature. Ligand exchange of the perchlorato ligands in (TMP·+)MnIII(ClO4)2 by chloride anions is accompanied by a change of the oxda on site from porphyrin to metal, resulting in (TMP)MnIV(Cl)2. This high-valent-metal complex can effect chlorine atom transfer to olefins, as well as to dimedone and chlorodimedone, natural substrates of chloroperoxidases.
Original language | English |
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Pages (from-to) | 3503-3511 |
Number of pages | 9 |
Journal | Inorganic Chemistry |
Volume | 36 |
Issue number | 16 |
DOIs | |
State | Published - 1 Jan 1997 |
Externally published | Yes |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry