M.S. / Chemistry / Resonance Raman spectra of the complex of FeIII-ethylenediamine-tetraacetate with hydrogen peroxide have been obtained in the region of the peroxidic O-O stretching vibration that occurs at 815 cm [superscript -1] in frozen solution. When the complex was prepared from nearly neat, mixed-isotope hydrogen peroxide, H216O18O, a single O-O vibration was observed at 794 cm [superscript -1]. This observation establishes that the two oxygen atoms of the bound peroxide are equivalent and that the peroxide is ligated in an η2 side-on configuration in this mononuclear complex. The absence of any shift in υ(O-O) when the complex was prepared in D2O solvent provides further support for the Fe-OO geometry and rules out the alternative η1 end-on Fe-OOH configuration. In contrast, υ(O-O) of free hydrogen peroxide in the frozen state occurs at 877 cm [superscript -1] in H2Oand at 879 cm [superscript -1] in D2O. The 2- cm [superscript -1] upshift in D2O is similar to that observed previously with oxyhemerythrin and appears to be characteristic of a hydrogen-bonded or protonated peroxide species.
| Identifer | oai:union.ndltd.org:OREGON/oai:content.ohsu.edu:etd/177 |
| Date | 09 1900 |
| Creators | Ahmad, Salman |
| Publisher | Oregon Health & Science University |
| Source Sets | Oregon Health and Science Univ. Library |
| Language | English |
| Detected Language | English |
| Type | Text |
| Format | Needs Adobe Acrobat Reader to view., pdf, 1477.006 KB |
| Rights | http://www.ohsu.edu/library/etd_rights.shtml |
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