The gas-phase photofragmentation of the mixed-ligand coordination compound trans-bis(trifluoroacetato)bis(N,N'-dimethylethylenediamine)nickel(II) (Ni(tfa)(2)(dmen)(2)) detected via time-of-flight mass spectrometry is reported. In contrast to most gas-phase studies of metal-containing compounds where fragmentation of weak metal-ligand bonds dominates, the data here show that the dmen ligands fragment while still coordinated to nickel. The manner in which these ligands fragment is highly specific, leading to mono- and diimine species that remain coordinated to nickel. Uncoordinated mono- and diimine species and various small dmen fragments are also observed with high intensities in the low mass region of the spectra. NiF+, a fragment that is formed by fluorine abstraction, is always observed, even though no Ni-F bonds exist in the starting material.