Comparative semiempirical study of oxygen binding to model iron complexes of phthalocyanine and porphyrin
- Univ. of Illinois, Chicago
Molecular electronic structures of the danions and iron complexes of phthalocyanine and related macrocyclic compounds (i.e., tetrabenzoporphyrin, tetraazaporphyrin, and porphyrin) which are of interest in electrocatalysis have been calculated with semiempirical all-valence electron methods. Significant differences are found between the electron distributions in phthalocyanine and porphyrin dianions due mainly to the nature of the atom bridging the indole or pyrrole ligands. Iron complexes of both macrocyclics also show significant electronic differences, with the iron atom in an intermediate spin state in phthalocyanine and a high spin state in porphyrin. Oxygen binding to the iron center in model compounds of both complexes was also studied. The side-on configuration appears to be preferred in the oxygen-phthalocyanine system and end-on bonding in the oxygen-porphyrin complex.
- OSTI ID:
- 6770796
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 86:22; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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CARBOXYLIC ACIDS
CATALYSIS
CATALYTIC EFFECTS
CHEMICAL BONDS
CHEMISTRY
COMPLEXES
DATA
DYES
ELECTROCHEMISTRY
ELECTRONIC STRUCTURE
ELEMENTS
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
IRON COMPLEXES
NONMETALS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN
PHTHALOCYANINES
PORPHYRINS
TRANSITION ELEMENT COMPLEXES