FeIII-Hydroperoxo and Peroxo Complexes with Aminopyridyl Ligands and the Resonance Raman Spectroscopic Identification of the Fe−O and O−O Stretching Modes

Experimentally calibrated computational chemistry of tryptophan hydroxylase: Trans influence, hydrogen-bonding, and 18-electron rule govern O2-activation

“…The vibration frequencies of the P his intermediate are lower than the O his (378 cm À1 and 849 cm À1 vs. 447 cm À1 and 918 cm À1 ), but still in the same range. These values are consistent with peroxo model complexes [59]. However, the frequencies of the P glu intermediate were calculated to 523 cm À1 and 1160 cm À1 .…”

“…[29]. For high-spin Fe III (O 2 ) complexes, Raman frequencies of m Fe-O = 465 cm À1 and m O-O = 820 cm À1 have been found [59]. The vibration frequencies of the P his intermediate are lower than the O his (378 cm À1 and 849 cm À1 vs. 447 cm À1 and 918 cm À1 ), but still in the same range.…”

Titanium-monosubstituted polyoxometalates: relation between homogeneous and heterogeneous Ti-single-site-based catalysis

“…If the proton were attached to the peroxo group, a characteristic H/D downshift of the RR band would be expected, as observed for iron hydroperoxo species [193,194]. Nevertheless, the 630 cm )1 feature appeared to be not sensitive to the replacement of H for D. Therefore, the RR labelling experiment is in agreement with the DFT calculations and confirms that in solid I the activating proton is most likely localised at the Ti-O-W bridge rather than at the peroxo group.…”

Non-heme iron polyazadentate complexes as catalysts for oxidations by H2O2: particular efficiency in aromatic hydroxylations and beneficial effects of a reducing agent

“…1), have been recently characterized [16][17][18], and found to react with H 2 O 2 with formation of Fe III OOH species that have been spectrally detected in the case of the (L 5 ) iron complexes [18,19]. Some of the L 4 3 iron complexes have been found to act as catalysts of hexane hydroxylation by O 2 in the presence of 2,3,5-trimethylhydroquinone as a reducing agent [16].…”