Bis-triazinyl pyridines (BTPs) exhibit solution selectivity for trivalent americium over lanthanides (Ln), the origins of which remain uncertain. Here, electrospray ionization was used to generate gas-phase complexes [ML3]3+, where M=La, Lu, or Am, and L is the BTP 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)-pyridine). Collision induced dissociation (CID) of [ML3]3+ in the presence of H2O yielded protonated ligand [L(H)]+, and hydroxide [ML2(OH)]2+ or hydrate [ML(L-H)(H2O)]2+ where (L-H)- is a deprotonated ligand. Whereas solution affinities indicate stronger binding of BTPs towards Am3+ versus Ln3+, the observed CID process is contrastingly more facile for M = Am versus Ln. To understand the disparity, density functional theory was employed to compute potential energy surfaces for two possible CID processes, for M = La and Am. In accord with the CID results, both the rate determining transition state barrier and the net energy are lower for [AmL3]3+ versus [LaL3]3+, and for both product isomers, [ML2(OH)]2+ and [ML(L-H)(H2O)]2+. More facile removal of a ligand from [AmL3]3+ by CID does not necessarily contradict stronger Am3+-L binding as inferred from solution behavior. In particular, the formation of new bonds in the products can distort kinetics and thermodynamics expected for simple bond cleavage reactions. In addition to correctly predicting the seemingly anomalous CID behavior, the computational results indicate greater participation of Am 5f versus La 4f orbitals in metal-ligand bonding.