Heme and nonheme-type flavone synthase enzymes, FS I and FS II are responsible for the synthesis of flavones, which play an important role in various biological processes, and have a wide range of biomedicinal properties including antitumor, antimalarial, and antioxidant activities. To get more insight into the mechanism of this curious enzyme reaction, nonheme structural and functional models were carried out by the use of mononuclear iron, [Fe^II(CDA-BPA*)]²⁺ (6) [CDA-BPA = N,N,N’,N’-tetrakis-(2-pyridylmethyl)-cyclohexanediamine], [Fe^II(CDA-BQA*)]²⁺ (5) [CDA-BQA = N,N,N’,N’-tetrakis-(2-quinolilmethyl)-cyclohexanediamine], [Fe^II(Bn-TPEN)(CH₃CN)]²⁺ (3) [Bn-TPEN = N-benzyl-N,N’,N’-tris(2-pyridylmethyl)-1,2-diaminoethane], [Fe^IV(O)(Bn-TPEN)]²⁺ (9), and manganese, [Mn^II(N4Py*)(CH₃CN)]²⁺ (2) [N4Py* = N,N-bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine)], [Mn^II(Bn-TPEN)(CH₃CN)]²⁺ (4) complexes as catalysts, where the possible reactive intermediates, high-valent Fe^IV(O) and Mn^IV(O) are known and well characterised. The results of the catalytic and stoichiometric reactions showed that the ligand framework and the nature of the metal cofactor significantly influenced the reactivity of the catalyst and its intermediate. Comparing the reactions of [Fe^IV(O)(Bn-TPEN)]²⁺ (9) and [Mn^IV(O)(Bn-TPEN)]²⁺ (10) towards flavanone under the same conditions, a 3.5-fold difference in reaction rate was observed in favor of iron, and this value is three orders of magnitude higher than was observed for the previously published [Fe^IV(O)(N2Py2Q*)]²⁺ [N,N-bis(2-quinolylmethyl)-1,2-di(2-pyridyl)ethylamine] species.

A series of divalent manganese complexes [M^II(HL^1–6)Cl₂] with the 1,3-bis(2’-Ar-imino)isoindolines (HLⁿ, n = 1–6, Ar = pyridyl, 4-methylpyridyl, imidazolyl, thiazolyl, benzimidazolyl and N-methylbenzimidazolyl, respectively) including the previously reported ligands (HL^{1–2, 4–6}) and complexes ([M^II(HL^1,5)Cl₂]) have been prepared and characterized by electrochemical and spectroscopic methods. In these complexes, it was possible to control the redox potential of the metal center by varying the aryl substituent on the bis-iminoisoindoline moiety, and investigate its effect in a catalase-like reaction, and oxidative bleaching process in buffered aqueous solution. The kinetics of the dismutation of H₂O₂ into H₂O and O₂, and the oxidative degradation of morin by H₂O₂ were investigated in buffered water, where the reactivity of the catalysts in both systems was markedly influenced by the redox and Lewis acidic properties of the metal centers and the concentration of the bicarbonate ions. Both the catalase-like and bleaching activity of the catalysts showed a linear correlation with the Mn^III/Mn^II redox potentials. The E_1/2 spans a 561 mV range from 388 mV (Ar = benzymidazolyl) to 948 mV (Ar = 4-methylpyridyl) vs. the SCE. The amount of bicarbonate is a critical issue for the in situ formation of peroxycarbonate as a versatile oxidant, and its participation in the formation of high valent Mn^IV = O species.

Non-heme manganese(II) complexes [(IndH)Mn^IICl₂] (1) and [(N4Py*)Mn^II(CH₃CN)](ClO₄)₂ (2) with tridentate isoindoline and pentadentate polypyridyl ligands (IndH = 1,3-bis(2′-pyridylimino)isoindoline; N4Py* = N,N-bis(2-pyridylmethyl)-1,2- di(2-pyridyl)ethylamine) proved to be suitable to catalyze the oxidative demethylation of N,N-dimethylaniline (DMA) with various oxidants such as tert-butyl hydroperoxide (TBHP), peracetic acid (PAA), and meta-chloroperoxybenzoic acid (mCPBA), resulting N-methylaniline (MA) as a main product with N-methylformanilide (MFA) as a result of a free-radical chain process under air. The effect of electron-donating and electron-withdrawing substituents on the aromatic ring on the relative reactivity of the substrates and on the product composition (MA/MFA) was also studied and showed a significant impact on the catalytic N-demethylation reaction. Based on the Hammett correlation with ρ = −0.38 (PAA), −0.45 (mCPBA), and −0.63 (TBHP) for 1 and ρ = −0.38 (PAA) and −0.37 (mCPBA) for 2, an electrophilic intermediate is suggested as the key oxidant. Furthermore, the spectral investigation (UV-Vis) resulted in direct evidence for the formation of a high-valent oxomanganese(IV) and a transient radical cation intermediate, p-Me-DMA^•+, suggesting that the initial step in the manganese-catalyzed oxidations is a fast electron-transfer between the amine and the high valent oxometal species. The mechanisms of the subsequent steps are discussed.