Electronic structure of iron phthalocyanine and its analogs: a theoretical study
Molecular electronic structures of the dianions and iron complexes of phthalocyanine and other macrocyclic compounds (i.e., tetrabenzoporphyrin, tetrazaporphyrin and porphyrin) which are of interest in oxygen electrocatalysis have been calculated using CNDO/INDO molecular orbital methods. Significatn differences are found between the electron distributions in phthalocyanine and porphyrin due mainly to a difference in the nature of the atom bridging the indole and pyrrole ligands. Both iron complexes of phthalocyanine and porphyrin have a quintuplet molecular electronic ground state with iron in an intermediate spin state in the former and high spin in the latter. Binding of oxygen to the iron center in model compounds of iron phthalocyanine and iron porphyrin was studied. Side-on configuration appears to be preferred in the oxygen-phthalocyanine system and end-on bonding in the oxygen-porphyrin complex. The effect of catalyst support, electron delocalization by dimerization, and protons in solution on the oxygen binding by iron phthalocyanine was also examined and preliminary results are described. 2 figures, 3 tables.
- Research Organization:
- Illinois Univ., Chicago (USA). Dept. of Chemistry; Argonne National Lab., IL (USA)
- DOE Contract Number:
- W-31109-ENG-38
- OSTI ID:
- 6434982
- Report Number(s):
- CONF-8105105-7; ON: DE83007590
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201 -- Chemical & Physicochemical Properties
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
AZOLES
CARBOXYLIC ACIDS
CATALYSTS
COMPLEXES
DATA
DYES
ELECTRONIC STRUCTURE
ENERGY LEVELS
GROUND STATES
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INDOLES
INFORMATION
IRON COMPLEXES
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHTHALOCYANINES
PORPHYRINS
PYRROLES
THEORETICAL DATA
TRANSITION ELEMENT COMPLEXES