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Fe-III-hydroperoxo and peroxo complexes with aminopyridyl ligands and the Resonance Raman spectroscopic identification of the Fe-O and O-O stretching modes
Citation key ISI:000088112600031
Author Simaan, A J and Dopner, S and Banse, F and Bourcier, S and Bouchoux, G and Boussac, A and Hildebrandt, P and Girerd, J J
Pages 1627-1633
Year 2000
ISSN 1434-1948
Journal Europ. J. Inorg. Chem.
Number 7
Month JUL
Abstract Nonheme Fe-III-hydroperoxo and Fe-III-peroxo complexes with aminopyridyl-type ligands have been prepared and characterized by UV/Vis, EPR, mass and Resonance Raman (RR) spectroscopy. The Fe-III(OOH) species are low-spin and exhibit a deep purple color due to the ligand-to-metal charge transfer (LMCT) band centered at ca. 550 nm. The RR spectra of the Fe-III(OOH) complexes display two bands at ca. 620 and 800 cm(-1) that are assigned to the respective Fe-O and O-O stretching modes on the basis of the characteristic H/D and O-16/O-18 frequency shifts. Upon deprotonation, Fe-III(O-2) species are obtained which possess a high-spin configuration of nearly axial symmetry and a LMCT transition in the near infrared (ca. 750 nm). The frequencies of the Fe-O and O-O stretching modes at ca. 465 and 820 cm(-1), as well as their respective O-16/O-18 shifts of -16 and -45 cm(-1), indicate an eta(2) coordination geometry for the Fe-III(O-2) complex.
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