Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
9591087 | Journal of Molecular Structure: THEOCHEM | 2005 | 8 Pages |
Abstract
The geometrical structures and electronic states of the reactive oxo species of iron (III) porphyrin chloride and its meso-tetraphenyl derivatives proposed as a synthetic model of oxidases were examined by using semi-empirical AM1 and PM3 parametrizations. The spin population for oxo-iron (IV) porphyrin Ï-cation radical (quartet, S=3/2) and its one-electron reduction species (triplet, S=1) were reproduced by both calculation methods irrespective of the presence of chloride ion as a sixth ligand. Mostly planar structures were obtained for iron porphyrins and their meso-tetraphenyl derivatives with four phenyl rings perpendicular to the porphyrin ring except when bromine atoms were introduced into β-positions. AM1 parametrization gave more appropriate orbital energies and spin population for both of the quartet and triplet oxo-iron (IV) species than PM3 and the electron-withdrawing phenyl groups in meso-positions were found to decrease the energy level of dÏ (Fe)-pÏ (O, Cl) orbitals being involved in the porphyrin-catalyzed oxidation.
Related Topics
Physical Sciences and Engineering
Chemistry
Physical and Theoretical Chemistry
Authors
Toshiyuki Katagi,