Formation pathway of a Mn(IV),Mn(IV) bis(μ-oxo) dimer that incorporates alkali and alkaline earth cations and electron transfer properties of the dimer

Colin P. Horwitz, Yangzhen Ciringh, Susan T. Weintraub

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

The oxidation of (3,3′-17-crown-6-SALPN)Mn(II) with O2 in CH3CN resulted in formation of the corresponding Mn(IV),Mn(IV) bis(μ-oxo) dimer (2). A 16O2/18O2 labeling experiment, in which the product was analyzed by FT-IR spectroscopy and electrospray ionization mass spectrometry (ESI-MS), showed no detectable quantity of the mixed-isotope product [(3,3′-17-crown-6(SALPN))Mn(IV)]2(μ- 16O)(μ-18O), suggesting a simple O-O bond cleavage/bis(μ-oxo) dimer formation pathway that does not include Mn-O monomers. Alkali or alkaline earth cations were incorporated into the crown ether portion of each ligand. Upon addition of 2 equiv. of NaPF6, KPF6, CaTf2, or BaTf2 (Tf is [SO3CF3]-) to a slurry of 2 in CH3CN, 2·2NaPF6, 2·2KPF6, 2·2CaTf2, or 2·2BaTf2 formed. All of the complexes were characterized by cyclic voltammetry. Anodic potential shifts were recorded for the Mn(IV),Mn(IV/III)(μ-O)2 and Mn(IV/III),Mn(III)(μ-O)2 redox processes upon cation incorporation into 2. The voltammetry of some of the complexes was suggestive of cation motion toward the Mn2O2 core following the injection of the first electron.

Original languageEnglish (US)
Pages (from-to)133-139
Number of pages7
JournalInorganica Chimica Acta
Volume294
Issue number2
DOIs
StatePublished - Nov 10 1999

Keywords

  • Dinuclear complexes
  • Manganese complexes
  • Oxidation
  • Schiff-base complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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