Electron spin resonance and electrospray ionization mass spectroscopic studies of the interaction of alkali and alkaline earth cations with manganese bis(μ-oxo) dimers

Colin P. Horwitz, Joseph T. Warden, Susan T. Weintraub

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The dimer [(3,3′-17-crown-6-SALPN)MnIV(μ-O)]2 (2) was prepared by the reaction of (3,3′-17-crown-6-SALPN)Mn(II) with O2 in CH3CN. Dimer 2 when reacted with two molar equivalents of NaPF6, KPF6, CaTf2 or BaTf2 (Tf- is SO3CF3-) formed the complexes 2·2NaPF6, 2·2KPF6, 2·2CaTf2 or 2·2BaTf2, respectively. The dimers were reduced to the mixed-valent MnIII,MnIV state either chemically with Cp2Co or electrochemically and their ESR spectra recorded. The ESR spectrum of each mixed-valent dimer showed a 16-line pattern characteristic of a valence trapped antiferromagnetically coupled species. The cation containing MnIV,MnIV bis(μ-oxo) dimers were also analyzed by electrospray ionization mass spectrometry using CH2Cl2 and CH3CN as solvents. Singly charged cations corresponding to the loss of one anion from the parent complex were observed for all four compounds. In addition, ions were detected in which cation exchange had occurred.

Original languageEnglish (US)
Pages (from-to)311-320
Number of pages10
JournalInorganica Chimica Acta
Issue number1-2 SPEC. ISSUE
StatePublished - May 1996



  • Dinuclear complexes
  • Electron spin resonance
  • Electrospray mass spectrometry
  • Manganese complexes
  • Oxo complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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