Abstract
Intramolecular H‐atom transfer in model peptide‐type radicals was investigated with high‐level quantum‐chemistry calculations. Examination of 1,2‐, 1,3‐, 1,5‐, and 1,6[C ↔ N]‐H shifts, 1,4‐ and 1,7[C ↔ C]‐H shifts, and 1,4[N ↔ N]‐H shifts (Scheme 1), was carried out with a number of theoretical methods. In the first place, the performance of UB3‐LYP (with the 6‐31G(d), 6‐31G(2df,p), and 6‐311+G(d,p) basis sets) and UMP2 (with the 6‐31G(d) basis set) was assessed for the determination of radical geometries. We found that there is only a small basis‐set dependence for the UB3‐LYP structures, and geometries optimized with UB3‐LYP/6‐31G(d) are generally sufficient for use in conjunction with high‐level composite methods in the determination of improved H‐transfer thermochemistry. Methods assessed in this regard include the high‐level composite methods, G3(MP2)‐RAD, CBS‐QB3, and G3//B3‐LYP, as well as the density‐functional methods B3‐LYP, MPWB1K, and BMK in association with the 6‐31+G(d,p) and 6‐311++G(3df,3pd) basis sets. The high‐level methods give results that are close to one another, while the recently developed functionals MPWB1K and BMK provide cost‐effective alternatives. For the systems considered, the transformation of an N‐centered radical to a C‐centered radical is always exothermic (by 25 kJ ⋅ mol^−1^ or more), and this can lead to quite modest barrier heights of less than 60 kJ ⋅ mol^−1^ (specifically for 1,5[C ↔ N]‐H and 1,6[C ↔ N]‐H shifts). H‐Migration barriers appear to decrease as the ring size in the transition structure (TS) increases, with a lowering of the barrier being found, for example when moving from a rearrangement proceeding via a four‐membered‐ring TS (e.g., the 1,3[C ↔ N]‐H shift, CH~3~C(O)NH^.^ → ^.^CH~2~C(O)NH~2~) to a rearrangement proceeding via a six‐membered‐ring TS (e.g., the 1,5[C ↔ N]‐H shift, ^.^NHCH~2~C(O)NHCH~3~ → NH~2~CH~2~C(O)NHCH~2~^.^).