Abstract
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.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.