Complexes of asparagine (Asn) cationized with Zn2+ and Cd2+ were examined by infrared multiple photon dissociation (IRMPD) action spectroscopy using light generated from a free electron laser. Electrospray ionization yielded complexes of deprotonated Asn with Zn2+, [Zn(Asn-H)](+), and intact Asn with CdCl+, CdCl+(Asn). Series of low energy conformers for each complex were found using quantum chemical calculations in order to identify the structures formed experimentally. The experimentally obtained spectra were compared to those calculated from optimized structures at the B3LYP/6-311+G(d,p) level for [Zn(Asn-H)](+) and the B3LYP/def2-TZVP level with an SDD effective core potential on cadmium for the CdCl+(Asn) system. The main binding motif observed for the CdCl+ complex is a charge solvated, tridentate [N, CO, COs] structure where the metal binds to the backbone amino group and carbonyl oxygens of the carboxylic acid and side-chain amide groups. The Zn2+ system deprotonates at the backbone carboxylic acid and prefers a [N, CO-, COs] binding motif, where binding was observed at the carboxylate site along with the backbone amino group and side-chain carbonyl groups. In both cases, the theoretically determined lowest-energy conformers explain the experimental [Zn(Asn-H)](+) and CdCl+ (Asn) spectra well. Additionally, complete mechanistic pathways were found for each of the major dissociation reactions of [Zn(Asn-H)](+) (primary loss of CO2, followed by the sequential loss of NH3) and CdCl+(Asn) (concomitant loss of NH3 + CO).