Multi-stage mass spectrometry (MSⁿ) on [(M + Ag − H)_x + Ag]⁺ precursor ions (where M = an amino acid such as glycine or N,N-dimethylglycine) results in the formation of stable silver (Ag₃⁺, Ag₅⁺ and Ag₇⁺) and silver hydride (Ag₂H⁺, Ag₄H⁺ and Ag₆H⁺) cluster cations in the gas phase. Deuterium labelling studies reveal that the source of the hydride can be either from the α carbon or from one of the heteroatoms. When M = glycine, the silver cyanide clusters Ag₄CN⁺ and Ag₅(H,C,N)⁺ are also observed. Collision induced dissociation (CID) and DFT calculations were carried out on each of these clusters to shed some light on their possible structures. CID of the Ag_n⁺ and Ag_n−1H⁺ clusters generally results in the formation of the same Ag_n−2⁺ product ions via the loss of Ag₂ and AgH respectively. DFT calculations also reveal that the Ag_n⁺ and Ag_n−1H⁺ clusters have similar structural features and that the Ag_n−1H⁺ clusters are only slightly less stable than their all silver counterparts. In addition, Ag_n⁺ and Ag_n−1H⁺ clusters react with 2-propanol and 2-butylamine via similar pathways, with multiple ligand addition occurring and a coupled deamination-dehydration reaction occurring upon condensation of a third (for Ag₂H⁺) or a fourth (for all other silver clusters) 2-butylamine molecule onto the clusters. Taken together, these results suggest that the Ag_n⁺ and Ag_n−1H⁺ clusters are structurally related via the replacement of a silver atom with a hydrogen atom. This replacement does not dramatically alter the cluster stability or its unimolecular or bimolecular chemistry with the 2-propanol and 2-butylamine reagents.