TY - JOUR
T1 - Conflicting Role of Water in the Activation of H2O2 and the Formation and Reactivity of Non-Heme FeIII-OOH and FeIII-O-FeIII Complexes at Room Temperature
AU - Padamati, Sandeep K.
AU - Draksharapu, Apparao
AU - Unjaroen, Duenpen
AU - Browne, Wesley R.
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/5/2
Y1 - 2016/5/2
N2 - The formation of an FeIII-OOH species by reaction of complex 1 ([(MeN3Py)FeII(CH3CN)2]2+) with H2O2 at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the FeIII-OOH species, and its subsequent conversion to relatively inert FeIII-O-FeIII species, is shown to be highly dependent on the concentration of water, with excess water favoring the formation of the latter species, which is studied by UV/vis absorption spectroelectrochemistry also. The presence of acetic acid increases the rate and extent of oxidation of 1 to its iron(III) state and inhibits the wasteful decomposition of H2O2 but does not affect significantly the spectroscopic properties of the FeIII-OOH species formed.
AB - The formation of an FeIII-OOH species by reaction of complex 1 ([(MeN3Py)FeII(CH3CN)2]2+) with H2O2 at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the FeIII-OOH species, and its subsequent conversion to relatively inert FeIII-O-FeIII species, is shown to be highly dependent on the concentration of water, with excess water favoring the formation of the latter species, which is studied by UV/vis absorption spectroelectrochemistry also. The presence of acetic acid increases the rate and extent of oxidation of 1 to its iron(III) state and inhibits the wasteful decomposition of H2O2 but does not affect significantly the spectroscopic properties of the FeIII-OOH species formed.
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U2 - 10.1021/acs.inorgchem.5b02976
DO - 10.1021/acs.inorgchem.5b02976
M3 - Article
C2 - 27074109
AN - SCOPUS:84968914447
SN - 0020-1669
VL - 55
SP - 4211
EP - 4222
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 9
ER -