Plasmodium falciparum in Ancient Egypt

The deprotonation of [FeIII(N4Py)(η1-OOH)]2+ 1 gives [FeIII(N4Py)(η2-OO)]+ 2, as unequivocally demonstrated by resonance Raman spectroscopy, and leads to the loss of alkane hydroxylation activity by 1.

Resonance Raman Evidence For The Interconversion Between An [Fe(III)èta1-OOH]2+ And [Fe(III)èta2-O2]+ Species And Mechanistic Implications Thereof

The deprotonation of [FeIII(N4Py)(èta1-OOH)]2+ 1 gives [FeIII(N4Py)(èta2-OO)]+2, as unequivocally demonstrated by resonance Raman spectroscopy, and leads to the loss of alkane hydroxylation activity by 1.

Iron Chemistry Of A Pentadentate Ligand That Generates A Metastable Fe(III)-OOH Intermediate: Supplementary Information CIF-file for C25H24Cl2FeN6O8

In an effort to gain more insight into the factors controlling the formation of low-spin non-heme FeIII-peroxo intermediates in oxidation catalysis, such as activated bleomycin, we have synthesized a series of iron complexes based on the pentadentate ligand N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-(bis-2-pyridylmethyl)amine). The following complexes have been prepared: [(N4Py)FeII(CH3CN)](ClO4)2 (1), [(N4Py)FeIICl](ClO4) (2), [(N4Py)-FeIIIOMe](ClO4)2 (3), and [(N4Py)2Fe2O](ClO4)4 (4). Complexes 1 and 2 have low- and high-spin FeII centers, respectively, whereas 3 is an FeIII complex that undergoes a temperature-dependent spin transition. The iron centers in the oxo-bridged dimer 4 are antiferromagnetically coupled (J = -104 cm-1). Comparison of the crystal structures of 1, 3, and 4 shows that the ligand is well suited to accommodate both FeII and FeIII in either spin state. For the high-spin FeIII complexes 3 and 4 the iron atoms are positioned somewhat outside of the cavity formed by the ligand, while in the case of the low-spin FeII complex 1 the iron atom is retained in the middle of the cavity with approximately equal bond lengths to all nitrogen atoms from the ligand. On the basis of UV/vis and EPR observations, it is shown that 1, 3, and 4 all react with H2O2 to generate the purple low-spin [(N4Py)-FeIIIOOH]2+ intermediate (6). In the case of 1, titration experiments with H2O2 monitored by UV/vis and 1H NMR reveal the formation of [(N4Py)FeIIIOH]2+ (5) and the oxo-bridged diiron(III) dimer (4) prior to the generation of the FeIII-OOH species (6). Raman spectra of 6 show distinctive Raman features, particularly a í (O-O) at 790 cm-1 that is the lowest observed for any iron-peroxo species. This observation may rationalize the reactivity of low-spin FeIII-OOH species such as “activated bleomycin”.