Chemical mechanism of dioxygen activation by manganese(III) Schiff base compound in the presence of aliphatic aldehydes

Miyuki Suzuki, Takashi Ishikawa, Akihiko Harada, Shigeru Ohba, Masatomi Sakamoto, Yuzo Nishida

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

The manganese(III) complexes with tetradentate Schiff base [H2(L)] derived from salicylaldehyde and 2-amino-1-benzylamine [abbreviated as H2(salabza)], ethylenedimaineand 2-hydroxybenzophenone [H2(7-Phe-salen)], ethylenediamine and 2-hydroxyacetophenone [H2(7-Me-salen)] showed much higher activity for degradation of tetraphenylcyclopentadienone(TCPN) the singlet oxygen (1Δg) scavenger, in the presence of cyclohexanecarboxaldehyde than those of the compounds with H2(salen) and H2(salphen), which are derived from salicyaldehyde and ethylenediamine, and o-phenylenediamine, respectively. X-ray crystal structural determinations of the former three compounds and electrochemical data of all the compounds have given strong support for the conclusion that the active species for degradation of TCPN is an acylperoxo MnIII species coordinated by an aliphatic peracid chelate, which should be derived from aliphatic aldehyde and dioxygen, where the geometry of the tetradentate Schiff base around the MnIII ion is of cis-β-configuration. Under the same experimental conditions, the corresponding iron(III) compounds exhibited negligible activity towards the activation of the dioxygen molecule. This was explained in terms of the difference in electronic structures between the two metal ions.

Original languageEnglish
Pages (from-to)2553-2561
Number of pages9
JournalPolyhedron
Volume16
Issue number15
DOIs
Publication statusPublished - 1997 Jan 1

Keywords

  • Activation of dioxygen
  • Dioxygen and aldehyde
  • Mn(III) Schiff base compounds
  • Mn(III) and Fe(III) compounds

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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