Protonation of Planar and Nonplanar Porphyrins: A Calorimetric and Computational Study

Herein, we report the first calorimetric study of the protonation of planar and nonplanar free-base porphyrins: H₂OETPP (strongly saddled by its substituents), H₂T(tBu)P (strongly ruffled by its substituents), and the nominally planar porphyrins (npPs) H₂OEP, H₂TPP, H₂T(nPe)P, and H₂T(iPr)P. The observed enthalpies of protonation in solution (ΔH_protsoln) for formation of the dications in 1,1,2,2-tetrachloroethane with 2% trifluoroacetic acid are −45 ± 1 kcal mol^–1 for the npPs, −52.0 kcal mol^–1 for H₂T(tBu)P, and −70.9 kcal mol^–1 for H₂OETPP. The corresponding enthalpies of protonation (ΔH_DFT) obtained from DFT calculations (−27 ± 5, −42, and −63 kcal mol^–1, respectively) reproduce this trend. The much more negative enthalpy of protonation seen for H₂OETPP is consistent with this molecule being pre-deformed into the saddle structure favored by porphyrin dications. Except for OETPP, the calculated enthalpies of the first protonations (ΔH₁) are significantly more positive than the enthalpies of the second protonations (ΔH₂). In addition, the structural strain energies for the first protonations (ΔE_st(1)) are also significantly more positive than ΔE_st(2). According to the calculations, the monocations thus have higher proton affinities than the corresponding free-base porphyrins due to a structural strain effect, which is consistent with the generally elusive nature of the porphyrin monocation. The recent observations of monocations for free-base porphyrins with a high degree of saddling can be rationalized in terms of ΔH₁ and ΔH₂ being similar; so, the monocation is no longer an unstable intermediate.