Spin Transition in a Manganese(III) Porphyrin Cation Radical, Its Transformation to a Dichloromanganese(IV) Porphyrin, and Chlorination of Hydrocarbons by the Latter

Lilia Kaustov, Merav E. Tal, Alexander I. Shames, Zeev Gross

Research output: Contribution to journalArticlepeer-review

47 Scopus citations

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 languageEnglish
Pages (from-to)3503-3511
Number of pages9
JournalInorganic Chemistry
Volume36
Issue number16
DOIs
StatePublished - 1 Jan 1997
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint

Dive into the research topics of 'Spin Transition in a Manganese(III) Porphyrin Cation Radical, Its Transformation to a Dichloromanganese(IV) Porphyrin, and Chlorination of Hydrocarbons by the Latter'. Together they form a unique fingerprint.

Cite this