Reactions of SO sub 2 with iron porphyrinates and the crystal structure of (hydrogen sulfato) (tetraphenylporphinato) iron(III) hemibenzene solvate

Journal Article · Wed Dec 28 04:00:00 EST 1988 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00299a010· OSTI ID:5305221

Scheidt, W R; Lee, Youngja; Finnegan, M G ^[1]

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1. Univ. of Notre Dame, IN (USA)

The reactions of Fe{sup II}TPP and Fe{sup III}TPP with sulfur dioxide have been investigated as part of a study of potential coordination chemistry models for sulfite and nitrite reductase. Although the solubility of Fe{sup II}TPP in a variety of solvents is significantly increased by the addition of SO{sub 2} to the solvent, the authors have been unable to isolate and SO{sub 2} adducts. We do find that the presence of SO{sub 2} substantially increases the oxidation sensitivity of iron(II) porphyrinates. The authors have isolated three different sulfato complexes of (porphinato)iron(III): the previously reported binuclear species, (Fe(TPP)){sub 2}SO{sub 4}, a mononuclear bisulfate complex, (Fe(TP-P)(OSO{sub 3}H)), and a third sulfate-containing derivative. The species have been characterized by UV-vis and IR spectroscopy, and the (Fe(TPP)(OSO{sub 3}H)) complex has also been the subject of a single-crystal X-ray structure determination. This investigation revealed a monodentate hydrogen sulfato ligand leading to a five-coordinate high-spin iron(III) complex. The axial Fe-O bond distance is 1.926 {angstrom}, and the average Fe-N bond distance is 2.042 {angstrom}. Crystal data for (Fe(TPP)(OSO{sub 3}H)){center dot}{1/2} C{sub 6}H{sub 6}: monoclinic, a = 16.981 (5) {angstrom}, b = 13.559 (3) {angstrom}, c = 33.456 (5) {angstrom}, {beta} = 99.88 (2){degree}, Z = 8, space group P2/c, 5990 unique observed data, R{sub 1} = 0.052, R{sub 2} = 0.059, all observations at 293 K. The reaction of sulfur trioxide with (Fe(TPP)){sub 2}O has also been briefly investigated: (Fe(TPP)){sub 2}SO{sub 4} is produced.

• OSTI ID: 5305221
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 27:26; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
AROMATICS
BENZENE
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
ENZYMES
HYDROCARBONS
INFRARED SPECTRA
IRON COMPLEXES
IRON COMPOUNDS
LIGANDS
MOLECULAR STRUCTURE
ORGANIC COMPOUNDS
OXIDATION
OXIDES
OXIDOREDUCTASES
OXYGEN COMPOUNDS
SOLUBILITY
SOLVENTS
SPECTRA
SPECTROSCOPY
STRUCTURAL CHEMICAL ANALYSIS
SULFUR COMPOUNDS
SULFUR DIOXIDE
SULFUR OXIDES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
ULTRAVIOLET SPECTRA