A rare mixed-valence state manganese(II/IV) tetranuclear cage formed using phenyl 2-pyridyl ketone oxime and azide as ligands

The reaction of Mn(O2CPh)2 · 2H2O with the sodium salt of phenyl 2-pyridyl ketone oxime and sodium azide in MeOH gives a tetranuclear cage with a [Mn3IIMnIV(μ4-O)(η1,μ2-N3)]7+ core. Magnetic and EPR studies show the cage has an S = 6 ground state.

The use of a reaction “blend” containing MnII, PhCO2-, phenyl 2-pyridyl ketone oxime and N3- leads to a new tetranuclear cage featuring the unprecedented [Mn3IIMnIV(μ4-O)(η1,μ2-N3)]7+ core with a 2 e− difference between the manganese oxidation states.Figure optionsDownload as PowerPoint slide