Nucleophilic Oxidation Reactions Research Articles

Unlocking Efficient Hydrogen Production: Nucleophilic Oxidation Reactions Coupled with Water Splitting.

Electrocatalytic water splitting driven by sustainable energy is a clean and promising water-chemical fuel conversion technology for the production of high-purity green hydrogen. However, the sluggish kinetics of anodic oxygen evolution reaction (OER) pose challenges for large-scale hydrogen production, limiting its efficiency and safety. Recently, the anodic OER has been replaced by a nucleophilic oxidation reaction (NOR) with biomass as the substrate and coupled with a hydrogen evolution reaction (HER), which has attracted great interest. Anode NOR offers faster kinetics, generates high-value products, and reduces energy consumption. By coupling NOR with hydrogen evolution reaction, hydrogen production efficiency can be enhanced while yielding high-value oxidation products or degrading pollutants. Therefore, NOR-coupled HER hydrogen production is another new green electrolytic hydrogen production strategy after electrolytic water hydrogen production, which is of great significance for realizing sustainable energy development and global decarbonization. This review explores the potential of nucleophilic oxidation reactions as an alternative to OER and delves into NOR mechanisms, guiding future research in NOR-coupled hydrogen production. It assesses different NOR-coupled production methods, analyzing reaction pathways and catalyst effects. Furthermore, it evaluates the role of electrolyzers in industrialized NOR-coupled hydrogen production and discusses future prospects and challenges. This comprehensive review aims to advance efficient and economical large-scale hydrogen production.

A New Domain of Reactivity for High-Valent Dinuclear [M(μ-O)2 M'] Complexes in Oxidation Reactions.

The strikingly different reactivity of a series of homo- and heterodinuclear [(MIII )(μ-O)2 (MIII )']2+ (M=Ni; M'=Fe, Co, Ni and M=M'=Co) complexes with β-diketiminate ligands in electrophilic and nucleophilic oxidation reactions is reported, and can be correlated to the spectroscopic features of the [(MIII )(μ-O)2 (MIII )']2+ core. In particular, the unprecedented nucleophilic reactivity of the symmetric [NiIII (μ-O)2 NiIII ]2+ complex and the decay of the asymmetric [NiIII (μ-O)2 CoIII ]2+ core through aromatic hydroxylation reactions represent a new domain for high-valent bis(μ-oxido)dimetal reactivity.

A New Domain of Reactivity for High‐Valent Dinuclear [M(μ‐O)2M′] Complexes in Oxidation Reactions

AbstractThe strikingly different reactivity of a series of homo‐ and heterodinuclear [(MIII)(μ‐O)2(MIII)′]2+ (M=Ni; M′=Fe, Co, Ni and M=M′=Co) complexes with β‐diketiminate ligands in electrophilic and nucleophilic oxidation reactions is reported, and can be correlated to the spectroscopic features of the [(MIII)(μ‐O)2(MIII)′]2+ core. In particular, the unprecedented nucleophilic reactivity of the symmetric [NiIII(μ‐O)2NiIII]2+ complex and the decay of the asymmetric [NiIII(μ‐O)2CoIII]2+ core through aromatic hydroxylation reactions represent a new domain for high‐valent bis(μ‐oxido)dimetal reactivity.

A mononuclear nonheme cobalt(iii)-hydroperoxide complex with an amphoteric reactivity in electrophilic and nucleophilic oxidative reactions.

A mononuclear nonheme cobalt(iii)-hydroperoxide complex bearing a tetramethylated cyclam ligand, [(12-TMC)Co(III)(OOH)](2+), was synthesized and characterized spectroscopically and computationally; the cobalt(iii)-hydroperoxide complex exhibited an amphoteric reactivity in electrophilic and nucleophilic oxidative reactions.

An amphoteric reactivity of a mixed-valent bis(μ-oxo)dimanganese(III,IV) complex acting as an electrophile and a nucleophile.

A mixed-valent bis(μ-oxo)dimanganese(III,IV) complex, [(dpaq)Mn(III)(O)2Mn(IV)(dpaq)](+) (1), was prepared by reacting a hydroxomanganese(III) complex, [(dpaq)Mn(III)(OH)](+), with hydrogen peroxide in the presence of triethylamine. The mixed-valent bis(μ-oxo)dimanganese(III,IV) complex (1) was well characterised by UV-vis, EPR and CSI-MS techniques. The electrophilic reactivity of 1 was investigated in the oxidation of 2,6-di-tert-butylphenol derivatives by 1, in which the relative rate afforded a good Hammett correlation with a ρ value of -1.0. The nucleophilic character of 1 was then investigated in aldehyde deformylation reactions, using 2-phenylpropionaldehyde (2-PPA) and benzaldehyde derivatives as substrates. In contrast to the case of the reaction of 1 with 2,6-di-tert-butylphenol derivatives, a positive ρ value of 0.89 was obtained in the Hammett plot, demonstrating that the bis(μ-oxo)-dimanganese(III,IV) complex is an active nucleophilic oxidant. Thus, 1 exhibited an amphoteric reactivity in both electrophilic and nucleophilic oxidative reactions.

Synthetic mononuclear nonheme iron-oxygen intermediates.

Mononuclear nonheme iron-oxygen species, such as iron-superoxo, -peroxo, -hydroperoxo, and -oxo, are key intermediates involved in dioxygen activation and oxidation reactions catalyzed by nonheme iron enzymes. Because these iron-oxygen intermediates are short-lived due to their thermal instability and high reactivity, it is challenging to investigate their structural and spectroscopic properties and reactivity in the catalytic cycles of the enzymatic reactions themselves. One way to approach such problems is to synthesize biomimetic iron-oxygen complexes and to tune their geometric and electronic structures for structural characterization and reactivity studies. Indeed, a number of biologically important iron-oxygen species, such as mononuclear nonheme iron(III)-superoxo, iron(III)-peroxo, iron(III)-hydroperoxo, iron(IV)-oxo, and iron(V)-oxo complexes, were synthesized recently, and the first X-ray crystal structures of iron(III)-superoxo, iron(III)-peroxo, and iron(IV)-oxo complexes in nonheme iron models were successfully obtained. Thus, our understanding of iron-oxygen intermediates in biological reactions has been aided greatly from the studies of the structural and spectroscopic properties and the reactivities of the synthetic biomimetic analogues. In this Account, we describe our recent results on the synthesis and characterization of mononuclear nonheme iron-oxygen complexes bearing simple macrocyclic ligands, such as N-tetramethylated cyclam ligand (TMC) and tetraamido macrocyclic ligand (TAML). In the case of iron-superoxo complexes, an iron(III)-superoxo complex, [(TAML)Fe(III)(O2)](2-), is described, including its crystal structure and reactivities in electrophilic and nucleophilic oxidative reactions, and its properties are compared with those of a chromium(III)-superoxo complex, [(TMC)Cr(III)(O2)(Cl)](+), with respect to its reactivities in hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) reactions. In the case of iron-peroxo intermediates, an X-ray crystal structure of an iron(III)-peroxo complex binding the peroxo ligand in a side-on (η(2)) fashion, [(TMC)Fe(III)(O2)](+), is described. In addition, iron(III)-peroxo complexes binding redox-inactive metal ions are described and discussed in light of the role of redox-inactive metal ions in O-O bond activation in cytochrome c oxidase and O2-evolution in photosystem II. In the case of iron-hydroperoxo intermediates, mononuclear nonheme iron(III)-hydroperoxo complexes can be generated upon protonation of iron(III)-peroxo complexes or by hydrogen atom abstraction (HAA) of hydrocarbon C-H bonds by iron(III)-superoxo complexes. Reactivities of the iron(III)-hydroperoxo complexes in both electrophilic and nucleophilic oxidative reactions are described along with a discussion of O-O bond cleavage mechanisms. In the last section of this Account, a brief summary is presented of developments in mononuclear nonheme iron(IV)-oxo complexes since the first structurally characterized iron(IV)-oxo complex, [(TMC)Fe(IV)(O)](2+), was reported. Although the field of nonheme iron-oxygen intermediates (e.g., Fe-O2, Fe-O2H, and Fe-O) has been developed greatly through intense synthetic, structural, spectroscopic, reactivity, and theoretical studies in the communities of bioinorganic and biomimetic chemistry over the past 10 years, there is still much to be explored in trapping, characterizing, and understanding the chemical properties of the key iron-oxygen intermediates involved in dioxygen activation and oxidation reactions by nonheme iron enzymes and their biomimetic compounds.

Crystallographic and spectroscopic characterization and reactivities of a mononuclear non-haem iron(III)-superoxo complex.

Mononuclear non-haem iron(III)-superoxo species (Fe(III)-O2(-·)) have been implicated as key intermediates in the catalytic cycles of dioxygen activation by non-haem iron enzymes. Although non-haem iron(III)-superoxo species have been trapped and characterized spectroscopically in enzymatic and biomimetic reactions, no structural information has yet been obtained. Here we report the isolation, spectroscopic characterization and crystal structure of a mononuclear side-on (η(2)) iron(III)-superoxo complex with a tetraamido macrocyclic ligand. The non-haem iron(III)-superoxo species undergoes both electrophilic and nucleophilic oxidation reactions, as well as O2-transfer between metal complexes. In the O2-transfer reaction, the iron(III)-superoxo complex transfers the bound O2 unit to a manganese(III) analogue, resulting in the formation of a manganese(IV)-peroxo complex, which is characterized structurally and spectroscopically as a mononuclear side-on (η(2)) manganese(IV)-peroxo complex. The difference in the redox distribution between the metal ions and O2 in iron(III)-superoxo and manganese(IV)-peroxo complexes is rationalized using density functional theory calculations.

Spectroscopic and computational characterization of CuII-OOR (R = H or cumyl) complexes bearing a Me6-tren ligand.

A copper(II)-hydroperoxo complex, [Cu(Me(6)-tren)(OOH)](+) (2), and a copper(ii)-cumylperoxo complex, [Cu(Me(6)-tren)(OOC(CH(3))(2)Ph)](+) (3), were synthesized by reacting [Cu(Me(6)-tren)(CH(3)CN)](2+) (1) with H(2)O(2) and cumyl-OOH, respectively, in the presence of triethylamine. These intermediates, 2 and 3, were successfully characterized by various physicochemical methods such as UV-vis, ESI-MS, resonance Raman and EPR spectroscopies, leading us to propose structures of the Cu(II)-OOR species with a trigonal-bipyramidal geometry. Density functional theory (DFT) calculations provided geometric and electronic configurations of 2 and 3, showing trigonal bipyramidal copper(II)-OOR geometries. These copper(II)-hydroperoxo and -cumylperoxo complexes were inactive in electrophilic and nucleophilic oxidation reactions.