High-yield epoxidations with hydrogen peroxide and tert-butyl hydroperoxide catalyzed by iron(III) porphyrins: heterolytic cleavage of hydroperoxides

cis-Dihydroxylation of Olefins by a Non-Heme Iron Catalyst: A Functional Model for Rieske Dioxygenases

“…This hypothesis is supported by the reactivity of another related iron complex, namely, [Fe II (bph)(CH 3 CN) 2 ](ClO 4 ) 2 (4, Figure 1), which catalyzes only alkene epoxidation ( Figure 1) and iron porphyrins also exhibit the same reactivity pattern (entries 9 ± 11). [10,11] Hence, two labile sites in cis positions on the iron center are required for cis-dihydroxylation activity of the iron catalyst in combination with H 2 O 2 . [20] Why are two labile sites in cis positions required for cis dihydroxylation of alkenes?…”

A view on the mechanism of metalloporphyrin degradation in hydrogen peroxide epoxidation reactions

“…The process of intramolecular catalyst destruction can involve the metallo-oxo intermediate (8) [20,27,28], but also a metallo-oxo intermediate (10) [29,30] which is formed from (8) by reaction with hydrogen peroxide [16,31]. Analogous processes have been suggested in iron metalloporphyrin catalysis [7,8] (Scheme 4).…”

“…One possibility is the intramolecular decomposition of the highly active species (path a) by a process similar to the described ring destruction in supported metalloporphyrins [14,15]. Other processes of macrocycle destruction of intermolecular nature are the oxidation of another molecule of catalyst by the active oxidant species (path b) or the generation of oxygen radical's by interaction with H 2 O 2 , which can destroy the catalyst (path c) [8,16] (Scheme 1).…”

Fe/Nanoporous Carbon Catalysts Obtained from Molasses for the Limonene Oxidation Process

“…Hydrogen peroxide and Fe 3+ undergo a redox cycle in which ·OH radicals are produced. Taking into account the results presented for the 0.68Fe/NPC, 1.32Fe/NPC and 2.64Fe/NPC catalysts, and the analysis of the literature data [31][32][33][34][35][36], the paths for the transformation of hydrogen peroxide in the presence Fe/NPC catalysts presented in Fig. 12 can be proposed.…”