Recently, I explored structurally straightforward pathways to C-alpha hydrogen atom, H-center dot, transfer reactions in the radical cation complex following electron capture/transfer of a series of polyprotonated peptides (J. Phys. Chem. A 2013, 117, 11891196). Here, I extend my analysis to incorporate detailed rearrangement processes potentially occurring prior to H-center dot transfer. This comprises intracomplex isomerization of the initial iminol-terminated (-C(OH)-NH) form of the c(n)' species to the energetically more favorable, amide-terminated form (-C(O)NH2) prior to C-alpha H-center dot abstraction by the z(m)center dot species. The data indicate that the previously published H-center dot transfer barriers are more energetically demanding than those of this multistep alternative. The rate-determining step is typically the intracomplex iminol isomerization, consistent with the substantial energetic favorability of the amide form of the c(n) species. The barriers to H-center dot transfer still rise steeply as a function of the charge state. In agreement with experiment, evidence for product separation without H-center dot transfer at a higher charge state is also provided.