Cα hydrogen atom transfer in post-cleavage radical-cation complexes: short and steep versus long winding road

Recently, I explored structurally straightforward pathways to Cα hydrogen atom, H(•), transfer reactions in the radical cation complex following electron capture/transfer of a series of polyprotonated peptides (J. Phys. Chem. A 2013, 117, 1189-1196). Here, I extend my analysis to incorporate detailed rearrangement processes potentially occurring prior to H(•) transfer. This comprises intracomplex isomerization of the initial iminol-terminated (-C(OH)═NH) form of the cn' species to the energetically more favorable, amide-terminated form (-C(O)-NH2) prior to Cα H(•) abstraction by the zm(•) species. The data indicate that the previously published H(•) 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 cn species. The barriers to H(•) transfer still rise steeply as a function of the charge state. In agreement with experiment, evidence for product separation without H(•) transfer at a higher charge state is also provided.