Manganese complexes exhibit a rich redox chemistry, usually accompanied by structural reorganization during the redox processes often followed by ligand dissociation or association. The push-pull ligand 2,6-diguanidylpyridine (dgpy) stabilizes manganese in the oxidation states +II, +III, and + IV in the complexes [Mn(dgpy)] ( = 2-4) without change in the coordination sphere in the condensed phase [Heinze et al., , 61, 14616]. In the condensed phase, the manganese(IV) complex is a very strong oxidant. In the present work, we investigate the stability and redox activity of the Mn complex and its counterion (PF) adducts in the gas phase, using two modified 3D Paul ion trap mass spectrometers. Six different cationic species of the type [Mn(dgpy)(PF)] ( = II, III, IV, = 0-3, = 1-3) could be observed for the three oxidation states Mn, Mn, and Mn, of which one observed complex also contains a reduced dgpy ligand. Mn species showed the highest relative stability in collision induced dissociation and UV/vis photo dissociation experiments. The lowest stability is observed in the presence of one or more counterions, which correlates to a lower total charge +. Gas phase UV/vis spectra show similar features as the condensed phase spectra only differing in relative band intensities. The strongly oxidizing Mn complex reacts with triethylamine (NEt) in the gas phase to give Mn, while Mn species show little reactivity toward NEt.
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