Complexes of Mn-II with 1,10-phenanthroline (phen) and 2,2'-bipyridine (bipy) are investigated by means of electrospray ionization (ESI) mass spectrometry. Under the conditions used, [MnLn](2+) with n = 2 and 3, [MnLnCl](+) with n = 0-2, and [Mn(2)LnCI(3)](+) with n = 2 and 3 are produced (where L = phen or bipy). The collision-induced dissociation (CID) spectra of the mass-selected ions show various dissociation pathways, most notable among them is the reduction of the ligated Mn-II to Mn-I by intracomplex electron transfer. CID experiments of mixed-ligand complexes formed upon ESI from solutions which contain both phen and bipy exhibit preferential eliminations of bipy, indicating that bipy is a significantly weaker ligand for Mn-II than phen. This effect is mainly attributed to the flexibility of the bipy ligand concomitant with thermodynamic control in ion dissociation. To support this hypothesis, mixed complexes with some methylated derivatives as well as those containing 4,5-diazafluorene (daf) are examined also. Interestingly, the differences between the ligands diminish in charge-separation reactions of dicationic Mn-II complexes, due to the joined operation of thermodynamic as well as kinetic effects. In addition, the complexes [Mn(bipy)](+), [Mn(phen)](+), [Mn(bipy)](2+), [Mn(phen)](2+), and [Mn(bipy)(phen)](2+) are computed using the mPW1PW91 hybrid density functional along with the Stuttgart-Cologne-type pseudopotential and basis-set suite, and relative energies for charge-separation reactions and losses of neutral ligands are evaluated.