A side-on Mn(III)-peroxo supported by a non-heme pentadentate N3Py2 ligand: synthesis, characterization and reactivity studies.

A mononuclear manganese(iii)-peroxo complex [MnIII(N3Py2)(O2)]+ (1a) bearing a non-heme N,N'-dimethyl-N-(2-(methyl(pyridin-2-ylmethyl)amino)ethyl)-N'-(pyridin-2-ylmethyl)ethane-1,2-diamine (N3Py2) ligand was synthesized by the reaction of [Mn(N3Py2)(H2O)](ClO4)2 (1) with hydrogen peroxide and triethylamine in CH3CN at 25 °C. The reactivity of 1a in aldehyde deformylation using 2-phenyl propionaldehyde (2-PPA) was studied and the reaction kinetics was monitored by UV-visible spectroscopy. A kinetic isotope effect (KIE) = 1.7 was obtained in the reaction of 1a with 2-PPA and α-[D1]-PPA, suggesting nucleophilic character of 1a. The activation parameters ΔH‡ and ΔS‡ were determined using the Eyring plot while Ea was obtained from the Arrhenius equation by performing the reaction between 288 and 303 K. Hammett constants (σp) of para-substituted benzaldehydes p-X-Ph-CHO (X = Cl, F, H, and Me) were linear with a slope (ρ) = 3.0. Computational study suggested that the side-on structure of 1a is more favored over the end-on structure and facilitates the reactivity of 1a.

MA2CoBr4: lead-free cobalt-based perovskite for electrochemical conversion of water to oxygen.

We have synthesized a lead-free stable organic-inorganic perovskite (MA2CoBr4) by using non-hazardous solvents such as methanol and ethanol, which are eco-friendly and safe to handle in comparison to DMF, toluene, etc. Single crystals of MA2CoBr4 were grown using a simple solution technique, and their electrochemical oxygen evolution was investigated in a wide pH range.

Autocatalytic dioxygen activation to produce an iron(v)-oxo complex without any reductants.

An iron(v)-oxo complex with a tetraamido macrocyclic ligand, [(TAML)FeV(O)]-, was produced by reacting [(TAML)FeIII]- with dioxygen without any electron source in acetone at 298 K. The autocatalytic mechanism of dioxygen activation for the formation of an iron(v)-oxo complex has been clarified based on the autocatalysis by radical chain initiators.

A Mononuclear Nonheme Iron(V)-Imido Complex.

Mononuclear nonheme iron(V)-oxo complexes have been reported previously. Herein, we report the first example of a mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [(TAML)FeV(NTs)]- (1). The spectroscopic characterization of 1 revealed an S = 1/2 Fe(V) oxidation state, an Fe-N bond length of 1.65(4) Å, and an Fe-N vibration at 817 cm-1. The reactivity of 1 was demonstrated in C-H bond functionalization and nitrene transfer reactions.

Influence of Ligand Architecture in Tuning Reaction Bifurcation Pathways for Chlorite Oxidation by Non-Heme Iron Complexes.

Reaction bifurcation processes are often encountered in the oxidation of substrates by enzymes and generally lead to a mixture of products. One particular bifurcation process that is common in biology relates to electron transfer versus oxygen atom transfer by high-valent iron(IV)-oxo complexes, which nature uses for the oxidation of metabolites and drugs. In biomimicry and bioremediation, an important reaction relates to the detoxification of ClOx- in water, which can lead to a mixture of products through bifurcated reactions. Herein we report the first three water-soluble non-heme iron(II) complexes that can generate chlorine dioxide from chlorite at ambient temperature and physiological pH. These complexes are highly active oxygenation oxidants and convert ClO2- into either ClO2 or ClO3¯ via high-valent iron(IV)-oxo intermediates. We characterize the short-lived iron(IV)-oxo species and establish rate constants for the bifurcation mechanism leading to ClO2 and ClO3- products. We show that the ligand architecture of the metal center plays a dominant role by lowering the reduction potential of the metal center. Our experiments are supported by computational modeling, and a predictive valence bond model highlights the various factors relating to the substrate and oxidant that determine the bifurcation pathway and explains the origins of the product distributions. Our combined kinetic, spectroscopic, and computational studies reveal the key components necessary for the future development of efficient chlorite oxidation catalysts.

A Manganese(V)-Oxo Complex: Synthesis by Dioxygen Activation and Enhancement of Its Oxidizing Power by Binding Scandium Ion.

A mononuclear non-heme manganese(V)-oxo complex, [Mn(V)(O)(TAML)](-) (1), was synthesized by activating dioxygen in the presence of olefins with weak allylic C-H bonds and characterized structurally and spectroscopically. In mechanistic studies, the formation rate of 1 was found to depend on the allylic C-H bond dissociation energies (BDEs) of olefins, and a kinetic isotope effect (KIE) value of 16 was obtained in the reactions of cyclohexene and cyclohexene-d10. These results suggest that a hydrogen atom abstraction from the allylic C-H bonds of olefins by a putative Mn(IV)-superoxo species, which is formed by binding O2 by a high-spin (S = 2) [Mn(III)(TAML)](-) complex, is the rate-determining step. A Mn(V)-oxo complex binding Sc(3+) ion, [Mn(V)(O)(TAML)](-)-(Sc(3+)) (2), was also synthesized in the reaction of 1 with Sc(3+) ion and then characterized using various spectroscopic techniques. The binding site of the Sc(3+) ion was proposed to be the TAML ligand, not the Mn-O moiety, probably due to the low basicity of the oxo group compared to the basicity of the amide carbonyl group in the TAML ligand. Reactivity studies of the Mn(V)-oxo intermediates, 1 and 2, in oxygen atom transfer and electron-transfer reactions revealed that the binding of Sc(3+) ion at the TAML ligand of Mn(V)-oxo enhanced its oxidizing power with a positively shifted one-electron reduction potential (ΔEred = 0.70 V). This study reports the first example of tuning the second coordination sphere of high-valent metal-oxo species by binding a redox-inactive metal ion at the supporting ligand site, thereby modulating their electron-transfer properties as well as their reactivities in oxidation reactions.

Enhanced Electron Transfer Reactivity of a Nonheme Iron(IV)-Imido Complex as Compared to the Iron(IV)-Oxo Analogue.

Reactions of N,N-dimethylaniline (DMA) with nonheme iron(IV)-oxo and iron(IV)-tosylimido complexes occur via different mechanisms, such as an N-demethylation of DMA by a nonheme iron(IV)-oxo complex or an electron transfer dimerization of DMA by a nonheme iron(IV)-tosylimido complex. The change in the reaction mechanism results from the greatly enhanced electron transfer reactivity of the iron(IV)-tosylimido complex, such as the much more positive one-electron reduction potential and the smaller reorganization energy during electron transfer, as compared to the electron transfer properties of the corresponding iron(IV)-oxo complex.

Influence of ligand architecture on oxidation reactions by high-valent nonheme manganese oxo complexes using water as a source of oxygen.

Mononuclear nonheme Mn(IV)=O complexes with two isomers of a bispidine ligand have been synthesized and characterized by various spectroscopies and density functional theory (DFT). The Mn(IV)=O complexes show reactivity in oxidation reactions (hydrogen-atom abstraction and sulfoxidation). Interestingly, one of the isomers (L(1) ) is significantly more reactive than the other (L(2) ), while in the corresponding Fe(IV)=O based oxidation reactions the L(2) -based system was previously found to be more reactive than the L(1) -based catalyst. This inversion of reactivities is discussed on the basis of DFT and molecular mechanics (MM) model calculations, which indicate that the order of reactivities are primarily due to a switch of reaction channels (σ versus π) and concomitant steric effects.

Long-range electron transfer triggers mechanistic differences between iron(IV)-oxo and iron(IV)-imido oxidants.

Nature often utilizes molecular oxygen for oxidation reactions through monoxygenases and dioxygenases. In many of these systems, a high-valent iron(IV)-oxo active species is found. In recent years, evidence has accumulated of possible iron(IV)-imido and iron(V)-nitrido intermediates in enzymatic catalysis, although little is known about their activity. In this work, we report a detailed combined kinetics and computational study on the difference in reactivity and chemical properties of nonheme iron(IV)-oxo compared with iron(IV)-tosylimido. We show here that iron(IV)-tosylimido complex is much more reactive with sulfides than the corresponding iron(IV)-oxo complex; however, the reverse trend is obtained for hydrogen atom abstraction reactions. The latter proceed with a relatively small kinetic isotope effect of kH/kD = 7 for the iron(IV)-tosylimido complex. Moreover, a Hammett analysis of hydrogen atom abstraction from para-X-benzyl alcohol reveals a slope of close to zero for the iron(IV)-oxo, whereas a strong negative slope is found for the iron(IV)-tosylimido complex. These studies implicate dramatic changes in the reaction mechanisms and suggest a considerable charge transfer in the transition states. Density functional theory calculations were performed to support the experiments and confirm an initial long-range electron transfer for the iron(IV)-tosylimido complex with substrates, due to a substantially larger electron affinity compared with the iron(IV)-oxo species. As a consequence, it also reacts more efficiently in electrophilic addition reactions such as those with sulfides. By contrast, the long-range electron transfer for the iron(IV)-tosylimido complex results in a rate constant that is dependent on the π*xz → σ*z(2) excitation energy, which raises the hydrogen atom abstraction barrier above that found for the iron(IV)-oxo. On the other hand, sulfimidation has much earlier electron transfer steps with respect to sulfoxidation. All data has been analyzed and rationalized with valence bond models and thermochemical cycles. Our studies highlight the catalytic potential of iron(IV)-tosylimido complexes in chemistry and biology.

Comparison of the reactivity of nonheme iron(IV)-oxo versus iron(IV)-imido complexes: which is the better oxidant?

Which is better? The first detailed comparison of the reactivity of nonheme iron(IV)-imido versus nonheme iron(IV)-oxo intermediates with substrates is presented. The iron(IV)-imido variant reacts with sulfides five times faster than iron(IV)-oxo, whereas the reverse trend is observed for hydrogen atom abstraction. These observed trends are analyzed and explained.

Mechanistic insight into halide oxidation by non-heme iron complexes. Haloperoxidase versus halogenase activity.

This work presents the first detailed study on mechanistic aspects of halide oxidation by non-heme iron complexes. We show that while iron(III)-hydroperoxo complexes oxidise halides via oxygen atom transfer, the corresponding iron(IV)-oxo complex reacts via electron transfer.

Nonheme ferric hydroperoxo intermediates are efficient oxidants of bromide oxidation.

This work presents the first combined experimental and computational study that gives evidence of the electrophilic reactivity of a nonheme iron(III)-hydroperoxo species. We show that in contrast to their heme counterparts the nonheme iron(III)-hydroperoxo complexes are catalytically much more active and even more so than nonheme iron(IV)-oxo species.