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Resonance Raman pursuit of the change from Fe sup II -O sub 2 to Fe sup III -OH via Fe sup IV = 0 in the autoxidation of ferrous iron-porphyrin

Journal Article · · Journal of the American Chemical Society; (United States)
DOI:https://doi.org/10.1021/ja00175a011· OSTI ID:5394491
;  [1];  [2];  [3]
  1. Okazaki National Research Institutes (Japan) Graduate Univ. for Advanced Studies, Okazaki (Japan)
  2. Okazaki National Research Institutes (Japan)
  3. Osaka Univ. (Japan)
+ Show Author Affiliations

Resonance Raman (RR) and visible absorption spectra were observed for autoxidation intermediates of ferrous tetramesitylporphyrin ((TMP)Fe{sup II}) to the ferric hydroxy derivative ((TMP)Fe{sup III}OH) via (TMP)Fe{sup II}O{sub 2}, (TMP)Fe{sup III}OOFe{sup III}(TMP), and (TMP)Fe{sup IV}{double bond}O. The O-O stretching ({nu}(O{sub 2})) and Fe{sup II}-O{sub 2} stretching ({nu}(Fe{sup II}-O{sub 2})) Raman bands were simultaneously observed at 1,171 and 522 cm{sup {minus}1}, respectively, for the (TMP)Fe{sup II}O{sub 2} in toluene solution at {minus}100{degree}C for the first time. The present data together with the reported IR data for the solution samples indicate a linear inverse correlation between {nu}(O{sub 2}) and {nu}(Fe{sup II}-O{sub 2}) frequencies similar to that between {nu}(CO) and {nu}(Fe{sup II}-CO), but the data from heme proteins fall off the line.

OSTI ID:
5394491
Journal Information:
Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 112:19; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
550200* -- Biochemistry
59 BASIC BIOLOGICAL SCIENCES
ABSORPTION SPECTRA
CARBOXYLIC ACIDS
ELEMENTS
ENZYMES
HEME
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
IRON
METALS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PIGMENTS
PORPHYRINS
PROTEINS
RAMAN SPECTRA
REACTION INTERMEDIATES
SPECTRA
TRANSITION ELEMENTS