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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
Author(s) -
Simaan A. Jalila,
Döpner Susanne,
Banse Frédéric,
Bourcier Sophie,
Bouchoux Guy,
Boussac Alain,
Hildebrandt Peter,
Girerd JeanJacques
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200007)2000:7<1627::aid-ejic1627>3.0.co;2-9
Subject(s) - physics , chemistry , raman spectroscopy , humanities , philosophy , optics
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 16 O/ 18 O 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 16 O/ 18 O shifts of −16 and −45 cm −1 , indicate an η 2 coordination geometry for the Fe III (O 2 ) complex.