Abstract
Transition metal cations Co^2+^, Ni^2+^ and Zn^2+^ form 1 : 1 : 1 ternary complexes with 2,2′‐bipyridine (bpy) and peptides in aqueous methanol solutions that have been studied for tripeptides GGG and GGL. Electrospray ionization of these solutions produced singly charged [Metal(bpy)(peptide − H)]^+^ and doubly charged [Metal(bpy)(peptide)]^2+^ ions (Metal = metal ion) that underwent charge reduction by glancing collisions with Cs atoms at 50 and 100 keV collision energies. Electron transfer to [Metal(bpy)(peptide)]^2+^ ions was less than 4.2 eV exoergic and formed abundant fractions of non‐dissociated charge‐reduced intermediates. Charge‐reduced [Metal(bpy)(peptide)]^+^ ions dissociated by the loss of a hydrogen atom, ammonia, water and ligands that depended on the metal ion. The Ni and Co complexes mainly dissociated by the elimination of ammonia, water, and the peptide ligand. The Zn complex dissociated by the elimination of ammonia and bpy. A sequence‐specific fragment was observed only for the Co complex. Electron transfer to [Metal(bpy)(peptide − H)]^+^ was 0.6–1.6 eV exoergic and formed intermediate radicals that were detected as stable anions after a second electron transfer from Cs. [Metal(bpy)(peptide − H)] neutrals and their anions dissociated by the loss of bpy and peptide ligands with branching ratios that depended on the metal ion. Optimized structures for several spin states, electron transfer and dissociation energies were addressed by combined density functional theory and Møller–Plesset perturbational calculations to aid interpretation of experimental data. The experimentally observed ligand loss and backbone cleavage in charge‐reduced [Metal(bpy)(peptide)]^+^ complexes correlated with the dissociation energies at the present level of theory. The ligand loss in ^+^CR^−^ spectra showed overlap of dissociations in charge‐reduced [Metal(bpy)(peptide − H)] complexes and their anionic counterparts which complicated spectra interpretation and correlation with calculated dissociation energies. Copyright © 2009 John Wiley & Sons, Ltd.