Chemistry and Physics Faculty Articles
Title
Protonation of Planar and Nonplanar Porphyrins: A Calorimetric and Computational Study
Document Type
Article
Publication Date
10-19-2020
Publication Title
The Journal of Physical Chemistry Part A
Keywords
Reaction mechanisms, Crystal structure, Pyrroles, Deformation, Enthalpy
ISSN
1089-5639
Abstract
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 (ΔHprotsoln) 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 (ΔHDFT) 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 (ΔEst(1)) are also significantly more positive than ΔEst(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.
Additional Comments
NIH grant #s: R24NS092986, EB027397, U24EB028941m S19-OD023592
NSUWorks Citation
Ballester, M., Ravotto, L., Quirke, J. E., de la Vega, R., Shelnutt, J. A., Cheprakov, A. V., Vinogradov, S. A., & Medforth, C. J. (2020). Protonation of Planar and Nonplanar Porphyrins: A Calorimetric and Computational Study. The Journal of Physical Chemistry Part A. https://doi.org/10.1021/acs.jpca.0c07610. Retrieved from https://nsuworks.nova.edu/cnso_chemphys_facarticles/281
DOI
10.1021/acs.jpca.0c07610
Comments
©2020 American Chemical Society