Comparative semiempirical study of oxygen binding to model iron complexes of phthalocyanine and porphyrin

Journal Article · Thu Oct 28 00:00:00 EDT 1982 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100219a013· OSTI ID:6770796

Sabelli, N H ^[1]; Melendres, C A

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1. 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), Vol. 86:22
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
08 HYDROGEN
IRON COMPLEXES
CATALYTIC EFFECTS
CHEMICAL BONDS
PHTHALOCYANINES
PORPHYRINS
CATALYSIS
ELECTROCHEMISTRY
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
OXYGEN
CARBOXYLIC ACIDS
CHEMISTRY
COMPLEXES
DATA
DYES
ELEMENTS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NONMETALS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
TRANSITION ELEMENT COMPLEXES
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