ESI tandem mass spectrometry is employed in a detailed study of the interactions of a hexameric duplex d(5'GCATGC) with three types of ligated first-row transition metal dications M2+: metallated bleomycins, singly, doubly, and triply ligated metallophenanthrolines and [M(triethylenetetramine)](2+). The singly, doubly, and triply metallated species were found to dissociate by noncovalent separation into two strands with metal ions attached either to one or to both. Relative gas-phase stabilities of the double-stranded oligodeoxynucleotide (ODN)-M2+ complexes were found to follow the order Mn(II) > Fe(II) > Co(II) > Ni(II) > Zn(II) > Cu(II). Overall, the presence of metal dications is found to increase the gas-phase stability of the duplex against noncovalent dissociation with the exception of one and three copper dications. An analysis of the dissociation pathways and relative gas-phase stabilities of the species that were investigated provided a basis for the assessment of the possible binding modes between duplex oligonucleotides and metallocomplexes.