ESR and resonance Raman spectroscopic studies of peroxide intermediates derived from iron diazaoxacyclononane.
A peroxide-Fe3+ intermediate generation during the Fenton reaction of iron chelate involving a ligating N,N'-di-2-picolyl-4, 7-diaza-1-oxacyclononane (DPC), H2O2/[Fe2+ DPC]2+, is reported. The identity of this peroxide complex is confirmed by resonance Raman (RR) and electron spin resonance (ESR) spectroscopies. The RR spectrum of [Fe2+ DPC]2+ treated with H2O2 shows a frequency at 854 cm(-1) ascribable to v(O-O) vibrational modes of the peroxide-Fe3+ complex with a side-on geometry. On the other hand, the ESR spectrum of H2O2/[Fe2+ DPC]2+ acquired at 77 K exhibits the resonance transition at g = 2.196 and 2.017 due to the peroxide-Fe3+ complex with an axial symmetry. It has been concluded that the H2O2/[Fe2+ DPC]2+ reaction proceeds by rapid bonding of H2O2 to an open coordination site on the central Fe2+ cation.
Szulbinski
W S
WS
Department of Environmental Monitoring, Central Institute of Mining, Plac Gwarków, Poland. scxws@gig.katowice.pl
D000473:Alkanes / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D005296:Ferrous Compounds / Q000737:chemistry*; D006573:Heterocyclic Compounds, 1-Ring / Q000737:chemistry*; D015394:Molecular Structure; D010545:Peroxides / Q000737:chemistry*; D013059:Spectrum Analysis, Raman
C419882:(N,N'-di-2-picolyl-4,7-diaza-1-oxacyclononane)iron(II); D000473:Alkanes; D005296:Ferrous Compounds; D006573:Heterocyclic Compounds, 1-Ring; D010545:Peroxides; C017573:nonane