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• W2161679472 endingPage "2343" @default.
• W2161679472 startingPage "2328" @default.
• W2161679472 abstract "Abstract High‐valent iron‐oxo species have been invoked as reactive intermediates in catalytic cycles of heme and nonheme enzymes. The studies presented herein are devoted to the formation of compound II model complexes, with the application of a water soluble (TMPS)Fe III (OH) porphyrin ([ meso ‐tetrakis(2,4,6‐trimethyl‐3‐sulfonatophenyl)porphinato]iron(III) hydroxide) and hydrogen peroxide as oxidant, and their reactivity toward selected organic substrates. The kinetics of the reaction of H 2 O 2 with (TMPS)Fe III (OH) was studied as a function of temperature and pressure. The negative values of the activation entropy and activation volume for the formation of (TMPS)Fe IV O(OH) point to the overall associative nature of the process. A pH‐dependence study on the formation of (TMPS)Fe IV O(OH) revealed a very high reactivity of OOH − toward (TMPS)Fe III (OH) in comparison to H 2 O 2 . The influence of N ‐methylimidazole ( N ‐MeIm) ligation on both the formation of iron(IV)‐oxo species and their oxidising properties in the reactions with 4‐methoxybenzyl alcohol or 4‐methoxybenzaldehyde, was investigated in detail. Combined experimental and theoretical studies revealed that among the studied complexes, (TMPS)Fe III (H 2 O)( N ‐MeIm) is highly reactive toward H 2 O 2 to form the iron(IV)‐oxo species, (TMPS)Fe IV O( N ‐MeIm). The latter species can also be formed in the reaction of (TMPS)Fe III ( N ‐MeIm) 2 with H 2 O 2 or in the direct reaction of (TMPS)Fe IV O(OH) with N ‐MeIm. Interestingly, the kinetic studies involving substrate oxidation by (TMPS)Fe IV O(OH) and (TMPS)Fe IV O( N ‐MeIm) do not display a pronounced effect of the N ‐MeIm axial ligand on the reactivity of the compound II mimic in comparison to the OH − substituted analogue. Similarly, DFT computations revealed that the presence of an axial ligand (OH − or N ‐MeIm) in the trans position to the oxo group in the iron(IV)‐oxo species does not significantly affect the activation barriers calculated for CH dehydrogenation of the selected organic substrates." @default.
• W2161679472 created "2016-06-24" @default.
• W2161679472 creator A5008794951 @default.
• W2161679472 creator A5021287965 @default.
• W2161679472 creator A5023399985 @default.
• W2161679472 creator A5035343648 @default.
• W2161679472 creator A5039203160 @default.
• W2161679472 creator A5080879830 @default.
• W2161679472 creator A5089141012 @default.
• W2161679472 creator A5090088124 @default.
• W2161679472 date "2014-01-17" @default.
• W2161679472 modified "2023-10-18" @default.
• W2161679472 title "Mechanistic Insight into Peroxo-Shunt Formation of Biomimetic Models for Compound II, Their Reactivity toward Organic Substrates, and the Influence of<i>N</i>-Methylimidazole Axial Ligation" @default.
• W2161679472 cites W158894830 @default.
• W2161679472 cites W1943768787 @default.
• W2161679472 cites W1963602830 @default.
• W2161679472 cites W1968400590 @default.
• W2161679472 cites W1969868637 @default.
• W2161679472 cites W1971268570 @default.
• W2161679472 cites W1976002718 @default.
• W2161679472 cites W1979975835 @default.
• W2161679472 cites W1984728399 @default.
• W2161679472 cites W1985266526 @default.
• W2161679472 cites W1988450367 @default.
• W2161679472 cites W1994780911 @default.
• W2161679472 cites W1997930564 @default.
• W2161679472 cites W1998514508 @default.
• W2161679472 cites W1999109626 @default.
• W2161679472 cites W1999826895 @default.
• W2161679472 cites W2001613444 @default.
• W2161679472 cites W2001740149 @default.
• W2161679472 cites W2004842749 @default.
• W2161679472 cites W2006307256 @default.
• W2161679472 cites W2007647406 @default.
• W2161679472 cites W2015523027 @default.
• W2161679472 cites W2017596140 @default.
• W2161679472 cites W2021406372 @default.
• W2161679472 cites W2023271753 @default.
• W2161679472 cites W2024254805 @default.
• W2161679472 cites W2025391537 @default.
• W2161679472 cites W2028177658 @default.
• W2161679472 cites W2031933469 @default.
• W2161679472 cites W2036524141 @default.
• W2161679472 cites W2036971596 @default.
• W2161679472 cites W2038533471 @default.
• W2161679472 cites W2039485473 @default.
• W2161679472 cites W2042920367 @default.
• W2161679472 cites W2044894178 @default.
• W2161679472 cites W2045016359 @default.
• W2161679472 cites W2045106489 @default.
• W2161679472 cites W2046123040 @default.
• W2161679472 cites W2047009021 @default.
• W2161679472 cites W2048241319 @default.
• W2161679472 cites W2048414598 @default.
• W2161679472 cites W2048455798 @default.
• W2161679472 cites W2049557754 @default.
• W2161679472 cites W2050169612 @default.
• W2161679472 cites W2055563809 @default.
• W2161679472 cites W2055624255 @default.
• W2161679472 cites W2057264761 @default.
• W2161679472 cites W2058210956 @default.
• W2161679472 cites W2059426878 @default.
• W2161679472 cites W2065278032 @default.
• W2161679472 cites W2065697991 @default.
• W2161679472 cites W2066795896 @default.
• W2161679472 cites W2067960609 @default.
• W2161679472 cites W2070947033 @default.
• W2161679472 cites W2071222585 @default.
• W2161679472 cites W2072730434 @default.
• W2161679472 cites W2073356400 @default.
• W2161679472 cites W2075396656 @default.
• W2161679472 cites W2075545064 @default.
• W2161679472 cites W2076246403 @default.
• W2161679472 cites W2077621515 @default.
• W2161679472 cites W2079202542 @default.
• W2161679472 cites W2080402236 @default.
• W2161679472 cites W2080887013 @default.
• W2161679472 cites W2083417559 @default.
• W2161679472 cites W2083662624 @default.
• W2161679472 cites W2086957099 @default.
• W2161679472 cites W2088976181 @default.
• W2161679472 cites W2091255628 @default.
• W2161679472 cites W2092634804 @default.
• W2161679472 cites W2097532911 @default.
• W2161679472 cites W2099872405 @default.
• W2161679472 cites W2100032379 @default.
• W2161679472 cites W2101505808 @default.
• W2161679472 cites W2104489411 @default.
• W2161679472 cites W2108116671 @default.
• W2161679472 cites W2131817082 @default.
• W2161679472 cites W2135733238 @default.
• W2161679472 cites W2136419697 @default.
• W2161679472 cites W2140158011 @default.
• W2161679472 cites W2143981217 @default.
• W2161679472 cites W2146702232 @default.
• W2161679472 cites W2147434133 @default.
• W2161679472 cites W2151975138 @default.
• W2161679472 cites W2165098689 @default.

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