TY  - JOUR
A1  - Wacker, Philipp
A1  - Dahms, Katja
A1  - Senge, Mathias O.
A1  - Kleinpeter, Erich
T1  - Conformational Landscape of meso-(1,3-Dithian-2-yl)porphyrins
N2  - An investigation of the conformational landscape of 1,3-dithian-2-yl bearing porphyrins and the rotational behavior of the dithianyl substituents in meso position was carried out by variable-temperature (VT) NMR spectroscopy. Additionally, theoretical results for alternative conformations and energy barriers were obtained by molecular modeling. The study revealed different NH trans tautomers with regard to the orientation of the dithianyl ligands for the free base porphyrins 1-3. Relatively ruffled porphyrin core conformations were established for the transition states of the dithianyl rotation, resulting in a lower rotational energy barrier for the nickel(II) complex 4 compared to that of the free base systems. The data obtained and the first depiction of a rotational transition state for the rotation of bulky meso-alkyl substituents illustrate the close structural interplay between meso-alkyl substituents and the macrocycle conformation in porphyrins.
Y1  - 2007
UR  - http://pubs.acs.org/doi/full/10.1021/jo0708700
U6  - https://doi.org/10.1021/Jo0708700
ER  -