Theoretical study of the inner hydrogen migration in the β-substituted 5,10,15,20-tetraphenylporphyrins.
In order to investigate the mechanism of the N-H migration in asymmetrical metal-free porphyrins, four porphyrins of electron-withdrawing or electron-donating substituent at the β-position were studied theoretically. For porphyrin 2 (R = OMe), 3 (R = Me), and 4 (R = NO(2)), four different asynchronous N-H migration pathways exist due to symmetry reasons. The corresponding trans-, cis-, and transition state geometries were analyzed using a normal structure decomposition method. Our data show that the hydrogen migration of porphyrin 2, 3, and 4 in clockwise (A, B) are much more preferred than counterclockwise (C, D) direction.
Key Laboratory of Bioelectrochemistry and Environmental Analysis of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070, China. taaluxq@gmail.com
Xiaoquan
X
Lu
Yong
Y
He
Jing
J
Chen
Jinfeng
J
Wang
Haicai
H
Shi
D006859:Hydrogen / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D011166:Porphyrins / Q000737:chemistry*; D011789:Quantum Theory
C509964:5,10,15,20-tetraphenylporphyrin; D011166:Porphyrins; D006859:Hydrogen