141070-28-2Relevant articles and documents
Synthesis, structure and characterisation of a new trinuclear di-μ-phenolato-μ-carboxylato MnIIIMnIIMn III complex with a bulky pentadentate ligand: Chemical access to mononuclear MnIV-OH entities
Hureau, Christelle,Anxolabehere-Mallart, Elodie,Blondin, Genevieve,Riviere, Eric,Nierlich, Martine
, p. 4808 - 4817 (2005)
A new trinuclear MnIIIMnIIMnIII complex has been isolated and X-ray characterised, namely [(py-salpn)Mn III(μ-OAc)-MnII(μ-OAc)MnIII(py-salpn)] 2+ (1), where H2py-salpn is the new bulky [N 3O2] ligand derived from the H2salpn Schiff base by the addition of one pyridine arm and the reduction of the imine function. The crystal structure reveals that the complex has a strictly 180° MnIII...MnII...MnIII angle, the MnII ion being located at an inversion centre. The complex is valence-trapped, with the terminal MnIII ions showing a Jahn-Teller elongation along the pyridine-MnIII-acetate axis. The Mn II...MnIII separation is 3.1224(13) A. The EPR spectra recorded on solid and frozen solutions are consistent with an Mn IIIMnIIMnIII species. The electrochemical response of complex 1 in acetonitrile solution exhibits two, one-electron reduction waves at E1/2 = 0.140 and -0.075 V vs. SCE. Phenolato and acetato→MnIII ligand-to-metal charge-transfer transitions are detected by UV/Visible spectroscopy at 359 and 587 nm, respectively. Chemical oxidation of an acetonitrile solution with tert-butyl hydroperoxide leads to mononuclear MnIV-hydroxo species, as evidenced by UV/Visible and EPR spectroscopy as well as ESI mass spectrometry. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
