A new MnII4MnIII4 cluster from the use of methyl 2-pyridyl ketone oxime in manganese carboxylate chemistry: Synthetic, structural and magnetic studies

Constantinos C. Stoumpos, Theocharis C. Stamatatos, Vassilis Psycharis, Catherine P. Raptopoulou, George Christou*, Spyros P. Perlepes

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Scopus citations

Abstract

The use of methyl 2-pyridyl ketone oxime (mpkoH) in manganese benzoate chemistry is reported. The reaction of Mn(O2CPh)2 · 2H2O with two equivalents of mpkoH in CH2Cl2 affords the mononuclear complex [MnII(O2CPh)2(mpkoH)2] (2) in high yield. The MnII atom is coordinated by two monodentate PhCO2- groups and two N,N′-bidentate mpkoH chelates in a cis-cis-trans fashion. Reaction mixtures comprising (NBun4)[MnIII4O 2(O2CPh)9(H2O)] and mpkoH in CH2Cl2, [MnIIMnIII2O(O2CPh) 6(py)2(H2O)] and mpkoH in CH2Cl2, or Mn(O2CPh)2 · 2H2O, NBun4 MnO4 and mpkoH in MeOH/MeCN/CH2Cl2 all lead to the mixed-valent cluster [MnII4MnIII4O2(OH )2(O2CPh)10(mpko)4] (3) in moderate yields. The cluster molecule has the [Mn84-O)23-OH) 2]14+ core (another description of the core is [Mn84-O)23-OH) 2(μ-OR′′)4(μ-ONR‴) 4]6+). Peripheral ligation is provided by two η1, four η11:μ and four η123PhCO2 - groups, as well as four η111:μ mpko- ligands. Variable-temperature, solid-state dc and ac magnetic studies were carried out on complex 3 in the 5.0-300 K (dc) and 1.8-10 K (ac) ranges. The data reveal dominant antiferromagnetic interactions and a resulting S = 0 ground state, which is rationalized in terms of the strong antiferromagnetic coupling within the central {Mn2III O2}2+ subunit.

Original languageEnglish (US)
Pages (from-to)3703-3709
Number of pages7
JournalPolyhedron
Volume27
Issue number18
DOIs
StatePublished - Dec 12 2008

Keywords

  • Crystal structures
  • Magnetochemistry
  • Manganese benzoate chemistry
  • Methyl 2-pyridyl ketone oxime metal complexes
  • Mixed-valent manganese clusters

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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