Metal-oxo Intermediates Research Articles

Intermolecular O-O Bond Formation between High-Valent Ru-oxo Species.

Despite extensive research on water oxidation catalysts over the past few decades, the relationship between high-valent metal-oxo intermediates and the O-O bond formation pathway has not been well clarified. Our previous study showed that the high spin density on O in RuV=O is pivotal for the interaction of two metal-oxyl radical (I2M) pathways. In this study, we found that introducing an axially coordinating ligand, which is favorable for bimolecular coupling, into the Ru-pda catalyst can rearrange its geometry. The shifts in geometric orientation altered its O-O bond formation pathway from water nucleophilic attack (WNA) to I2M, resulting in a 70-fold increase in water oxidation activity. This implies that the I2M pathway is concurrently influenced by the spin density on oxo and the geometry organization of the catalysts. The observed mechanistic switch and theoretical studies provide insights into controlling reaction pathways for homogeneous water oxidation catalysis.

Mechanistic insights into multimetal synergistic and electronic effects in a hexanuclear iron catalyst with a [Fe3(μ3-O)(μ2-OH)]2 core for enhanced water oxidation.

Multinuclear molecular catalysts mimicking natural photosynthesis have been shown to facilitate water oxidation; however, such catalysts typically operate in organic solutions, require high overpotentials and have unclear catalytic mechanisms. Herein, a bio-inspired hexanuclear iron(III) complex I, Fe6(μ3-O)2(μ2-OH)2(bipyalk)2(OAc)8 (H2bipyalk = 2,2'-([2,2'-bipyridine]-6,6'-diyl)bis(propan-2-ol); OAc = acetate) with desirable water solubility and stability was designed and used for water oxidation. Our results showed that I has high efficiency for water oxidation via the water nucleophilic attack (WNA) pathway with an overpotential of only ca. 290 mV in a phosphate buffer of pH 2. Importantly, key high-oxidation-state metal-oxo intermediates formed during water oxidation were identified by in situ spectroelectrochemistry and oxygen atom transfer reactions. Theoretical calculations further supported the above identification. Reversible proton transfer and charge redistribution during water oxidation enhanced the electron and proton transfer ability and improved the reactivity of I. Here, we have shown the multimetal synergistic and electronic effects of catalysts in water oxidation reactions, which may contribute to the understanding and design of more advanced molecular catalysts.

Whose Oxygen Atom Is Transferred to the Products? A Case Study of Peracetic Acid Activation via Complexed MnII for Organic Contaminant Degradation.

Identifying reactive species in advanced oxidation process (AOP) is an essential and intriguing topic that is also challenging and requires continuous efforts. In this study, we exploited a novel AOP technology involving peracetic acid (PAA) activation mediated by a MnII-nitrilotriacetic acid (NTA) complex, which outperformed iron- and cobalt-based PAA activation processes for rapidly degrading phenolic and aniline contaminants from water. The proposed MnII/NTA/PAA system exhibited non-radical oxidation features and could stoichiometrically oxidize sulfoxide probes to the corresponding sulfone products. More importantly, we traced the origin of O atoms from the sulfone products by 18O isotope-tracing experiments and found that PAA was the only oxygen-donor, which is different from the oxidation process mediated by high-valence manganese-oxo intermediates. According to the results of theoretical calculations, we proposed that NTA could tune the coordination circumstance of the MnII center to elongate the O-O bond of the complexed PAA. Additionally, the NTA-MnII-PAA* molecular cluster presented a lower energy gap than the MnII-PAA complex, indicating that the MnII-peroxy complex was more reactive in the presence of NTA. Thus, the NTA-MnII-PAA* complex exhibited a stronger oxidation potential than PAA, which could rapidly oxidize organic contaminants from water. Further, we generalized our findings to the CoII/PAA oxidation process and highlighted that the CoII-PAA* complex might be the overlooked reactive cobalt species. The significance of this work lies in discovering that sometimes the metal-peroxy complex could directly oxidize the contaminants without the further generation of high-valence metal-oxo intermediates and/or radical species through interspecies oxygen and/or electron transfer.

Mechanistic Insights into Cobalt-Based Water Oxidation Catalysis by DFT-Based Molecular Dynamics Simulations.

We report the mechanistic details of the water oxidation process by the complex, [CoII(bpbH2)Cl2], where bpbH2 = N, N'-bis(2'-pyridinecarboxamide)-1,2-benzene. An experimental study reported the complex as the efficient catalyst for the water oxidation process. We performed density functional theory calculations at the M06-L level and first-principles molecular dynamics simulations to study the catalytic nature of the complex. We investigated the energetics of the total catalytic cycle, which combines the oxygen-oxygen bond formation, proton-coupled electron transfer (PCET) steps, and release of oxygen molecule. The formed peroxide and superoxide intermediates in the catalytic cycle were characterized with the help of the Mulliken spin density parameters. Mulliken spin densities of the metal-oxo bond reveal that the triplet state of CoV═O has a double-bond nature, but the quintet state of the complex has a radical nature (CoIV-O•-). In an alternative way, the deprotonation of the amide groups of the ligand is also considered. The deprotonation and formation of higher oxidation metal-oxo intermediates are also possible. In addition to this, we have considered the effect of phosphate buffer on water nucleophilic addition. The oxygen-oxygen bond formation is favorable by the catalyst with the deprotonated form of the ligand, with the addition of water as the nucleophile. In the oxidation process, the C═O bonds of the ligand transfer the electron density to nitrogen atoms, stabilizing the higher order oxo, peroxide, and superoxide bonds. The oxygen-oxygen bond formation is the rate-determining step in the overall water oxidation process. This bond was further investigated using first-principles molecular dynamics at the PBE-D2 level. The dynamics of proton, hydroxide ion, and the nature of the ligand structure on the oxygen-oxygen bond were examined. We find that the oxygen molecule is released from the superoxide complex with the addition of water molecules.

Bisulfite activated permanganate for oxidative water decontamination

Recently, bisulfite-activated permanganate (MnO4−; Mn(VII)) process has attracted considerable attention as a novel class of advanced oxidation technology for destruction of organic contaminants in water. However, disputes over the underlying activation mechanism as well as reactive species generated in the Mn(VII)/bisulfite system remain for a long period due to the fairly complex chemistry involved in this system. This article aims to present a critical review on scientific development of the Mn(VII)/bisulfite system, with particular focus on the generation and contribution of various reactive intermediates. Both reactive manganese species (RMnS) (i.e., soluble Mn(III), Mn(V), and Mn(VI)) and radical species (primarily SO4•−) are identified as the oxidizing components responsible for enhanced degradation of organic contaminants by the Mn(VII)/bisulfite system. Bisulfite plays a dual role of being an activating agent for reactive intermediates generation and acting as a complexing agent to stabilize RMnS. Solution chemistry (e.g., the [Mn(VII)]/[bisulfite] molar ratio, solution pH, the type of contaminants, ligands, and water matrix components) greatly impacts the generation and consumption of RMnS and radicals, thus influencing the degradation kinetics and pathways of organics. Particularly, dissolved oxygen (DO) is a vital factor for driving the oxidation of organics since the absence of DO can block the generation of SO4•− and meantime causes the consumption of RMnS by excess SO3•− as a strong reductant. Interestingly, ferrate (FeO42−, Fe(VI)) and hexavalent chromium (CrO42−/HCrO4−, Cr(VI)) that are high-valent metal oxyanions analogous to Mn(VII) can be activated by bisulfite via a similar pathway (i.e. both high-valent metal-oxo intermediates and reactive radicals are involved). Furthermore, key knowledge gaps are identified and future research needs are proposed to address the potential challenges encountered in practical application of the Mn(VII)/bisulfite oxidation technology.

Differences in chemoselectivity in olefin oxidation by a series of non-porphyrin manganese(IV)-oxo complexes.

High valent metal-oxo intermediates are versatile oxidants known to facilitate both oxygen atom transfer (OAT) and hydrogen atom transfer (HAT) reactions in nature. In addition to performing essential yet challenging biological reactions, these intermediates are known for their selectivity in favoring the formation of one oxidation product. To understand the basis for this selectivity, we explore the role of equatorial ligand field perturbations in MnIV-oxo complexes on chemoselectivity in cyclohexene oxidation. We also examine reactions of MnIV-oxo complexes with cyclohexene-d10, cyclooctene, and styrene. Within this series, the product distribution in olefin oxidation is highly dependent on the coordination environment of the MnIV-oxo unit. While MnIV-oxo complexes with sterically encumbered, and slightly tilted, MnO units favor CC epoxidation products in cyclohexene oxidation, a less encumbered analogue prefers to cleave allylic C-H bonds, resulting in cyclohexenol and cyclohexenone formation. These conclusions are drawn from GC-MS product analysis of the reaction mixture, changes in the UV-vis absorption spectra, and kinetic analyses. DFT computations establish a trend in thermodynamic properties of the MnIV-oxo complexes and their reactivity towards olefin oxidation on the basis of the MnO bond dissociation free energy (BDFE). The most reactive MnIV-oxo adduct from this series oxidizes cyclohexene-d10, cyclooctene, and styrene to give corresponding epoxides as the only detected products. Collectively, these results suggest that the chemoselectivity obtained in oxidation of olefins is controlled by both the coordination environment around the MnO unit, which modulates the MnO BDFE, and the BDFEs of the allylic C-H bond of the olefins.

Enzyme-Like Hydroxylation of Aliphatic C-H Bonds From an Isolable Co-Oxo Complex.

The selective hydroxylation of aliphatic C-H bonds remains a challenging but broadly useful transformation. Nature has evolved systems that excel at this reaction, exemplified by cytochrome P450 enzymes, which use an iron-oxo intermediate to activate aliphatic C-H bonds with k1 > 1400 s-1 at 4 °C. Many synthetic catalysts have been inspired by these enzymes and are similarly proposed to use transition metal-oxo intermediates. However, most examples of well-characterized transition metal-oxo species are not capable of reacting with strong, aliphatic C-H bonds, resulting in a lack of understanding of what factors facilitate this reactivity. Here, we report the isolation and characterization of a new terminal CoIII-oxo complex, PhB(AdIm)3CoIIIO. Upon oxidation, a transient CoIV-oxo intermediate is generated that is capable of hydroxylating aliphatic C-H bonds with an extrapolated k1 for C-H activation >130 s-1 at 4 °C, comparable to values observed in cytochrome P450 enzymes. Experimental thermodynamic values and DFT analysis demonstrate that, although the initial C-H activation step in this reaction is endergonic, the overall reaction is driven by an extremely exergonic radical rebound step, similar to what has been proposed in cytochrome P450 enzymes. The rapid C-H hydroxylation reactivity displayed in this well-defined system provides insight into how hydroxylation is accomplished by biological systems and similarly potent synthetic oxidants.

Intramolecular Hydrogen-Bond Interactions Tune Reactivity in Biomimetic Bis(μ-hydroxo)dicobalt Complexes.

Active site hydrogen-bond (H-bond) networks represent a key component by which metalloenzymes control the formation and deployment of high-valent transition metal-oxo intermediates. We report a series of dinuclear cobalt complexes that serve as structural models for the nonheme diiron enzyme family and feature a Co2(μ-OH)2 diamond core stabilized by intramolecular H-bond interactions. We define the conditions required for the kinetically controlled synthesis of these complexes: [Co2(μ-OH)2(μ-OAc)(κ1-OAc)2(pyR)4][PF6] (1R), where OAc = acetate and pyR = pyridine with para-substituent R, and we describe a homologous series of 1R in which the para-R substituent on pyridine is modulated. The solid state X-ray diffraction (XRD) structures of 1R are similar across the series, but in solution, their 1H NMR spectra reveal a linear free energy relationship (LFER) where, as R becomes increasingly electron-withdrawing, the intramolecular H-bond interaction between bridging μ-OH and κ1-acetate ligands results in increasingly "oxo-like" μ-OH bridges. Deprotonation of the bridging μ-OH results in the quantitative conversion to corresponding cubane complexes: [Co4(μ-O)4(μ3-OAc)4(pyR)4] (2R), which represent the thermodynamic sink of self-assembly. These reactions are unusually slow for rate-limiting deprotonation events, but rapid-mixing experiments reveal a 6000-fold rate acceleration on going from R = OMe to R = CN. These results suggest that we can tune reactivity by modulating the μ-OH pKa in the presence of intramolecular H-bond interactions to maintain stability as the octahedral d6 centers become increasingly acidic. Nature may similarly employ dynamic carboxylate-mediated H-bond interactions to control the reactivity of acidic transition metal-oxo intermediates.

Mechanistic Insight into the O2 Evolution Catalyzed by Copper Complexes with Tetra- and Pentadentate Ligands

The mononuclear complexes ([(bztpen)Cu] (BF4)2 (bztpen = N-benzyl-N,N',N'-tris (pyridin-2-yl methyl ethylenediamine))) and ([(dbzbpen)Cu(OH2)] (BF4)2 (dbzbpen = N,N'-dibenzyl-N,N'-bis(pyridin-2-ylmethyl) ethylenediamine)) have been reported as water oxidation catalysts in basic medium (pH = 11.5). We explore the O2 evolution process catalyzed by these copper catalysts with various ligands (L) by applying the first-principles molecular dynamics simulations. First, the oxidation of catalysts to the metal-oxo intermediates [LCu(O)]2+ occurs through the proton-coupled electron transfer (PCET) process. These intermediates are involved in the oxygen-oxygen bond formation through the water-nucleophilic addition process. Here, we have considered two types of oxygen-oxygen bond formation. The first one is the transfer of the hydroxide of the water molecule to the Cu═O moiety; the proton transfer to the solvent leads to the formation of the peroxide complex ([LCu(OOH)]+). The other is the formation of the hydrogen peroxide complex ([LCu(HOOH)]2+) by the transfer of proton and hydroxide of the water molecule to the metal-oxo intermediate. The formation of the peroxide complex requires less activation free energy than hydrogen peroxide formation for both catalysts. We found two transition states in the well-tempered metadynamics simulations: one for proton transfer and another for hydroxide transfer. In both cases, the proton transfer requires higher free energy. Following the formation of the oxygen-oxygen bond, we study the release of the dioxygen molecule. The formed peroxide and hydrogen peroxide complexes are converted into the superoxide complex ([LCu(OO)]2+) through the transfer of proton, electron, and PCET processes. The superoxide complex releases an oxygen molecule upon the addition of a water molecule. The free energy of activation for the release of the dioxygen molecule is lesser than that of the oxygen-oxygen bond formation. When we observe the entire water oxidation process, the oxygen-oxygen bond formation is the rate-determining step. We calculated the rates of reaction by using the Eyring equation and found them to be close to the experimental values.

A Noncanonical Tryptophan Analogue Reveals an Active Site Hydrogen Bond Controlling Ferryl Reactivity in a Heme Peroxidase.

Nature employs high-energy metal-oxo intermediates embedded within enzyme active sites to perform challenging oxidative transformations with remarkable selectivity. Understanding how different local metal-oxo coordination environments control intermediate reactivity and catalytic function is a long-standing objective. However, conducting structure–activity relationships directly in active sites has proven challenging due to the limited range of amino acid substitutions achievable within the constraints of the genetic code. Here, we use an expanded genetic code to examine the impact of hydrogen bonding interactions on ferryl heme structure and reactivity, by replacing the N–H group of the active site Trp51 of cytochrome c peroxidase by an S atom. Removal of a single hydrogen bond stabilizes the porphyrin π-cation radical state of CcP W191F compound I. In contrast, this modification leads to more basic and reactive neutral ferryl heme states, as found in CcP W191F compound II and the wild-type ferryl heme-Trp191 radical pair of compound I. This increased reactivity manifests in a >60-fold activity increase toward phenolic substrates but remarkably has negligible effects on oxidation of the biological redox partner cytc. Our data highlight how Trp51 tunes the lifetimes of key ferryl intermediates and works in synergy with the redox active Trp191 and a well-defined substrate binding site to regulate catalytic function. More broadly, this work shows how noncanonical substitutions can advance our understanding of active site features governing metal-oxo structure and reactivity.

Observation of a potential-dependent switch of water-oxidation mechanism on Co-oxide-based catalysts

Summary O–O bond formation is a key elementary step of the water-oxidation reaction. However, it is still unclear how the mechanism of O–O coupling depends on the applied electrode potential. Herein, using water-in-salt electrolytes, we systematically altered the water activity, which enabled us to probe the O–O bond-forming mechanism on heterogeneous Co-based catalysts as a function of applied potential. We discovered that the water-oxidation mechanism is sensitive to the applied potential: At relatively low driving force, the reaction proceeds through an intramolecular oxygen coupling mechanism, whereas the water nucleophilic attack mechanism prevails at high driving force. The observed mechanistic switch has major implications for the understanding and control of the water-oxidation reaction on heterogeneous catalysts.

Visible light-induced oxidative N-dealkylation of alkylamines by a luminescent osmium(vi) nitrido complex.

N-Dealkylation of amines by metal oxo intermediates (M Created by potrace 1.16, written by Peter Selinger 2001-2019 ]]> O) is related to drug detoxification and DNA repair in biological systems. In this study, we report the first example of N-dealkylation of various alkylamines by a luminescent osmium(vi) nitrido complex induced by visible light.

Why Conventional Design Rules for C–H Activation Fail for Open-Shell Transition-Metal Catalysts

The design of selective and active C–H activation catalysts for direct methane-to-methanol conversion is challenging. Bioinspired complexes that form high-valent metal–oxo intermediates capable of hydrogen abstraction and rebound hydroxylation are promising candidates. This promise has made them a target for computational high-throughput screening, typically simplified through the use of linear free energy relationships (LFERs). However, their mid-row transition-metal centers have numerous accessible spin and oxidation states that increase the combinatorial scale of design efforts. Here, we carry out a computational design screen of over 2500 mid-row 3d transition-metal complexes with four metals in numerous spin and oxidation states. We demonstrate the importance of spin/oxidation state in dictating design principles, limiting the generalization of strategies derived for widely studied high-spin Fe(II) catalysts to other metals or spin/oxidation states. Combined assessment of the effect of ligand-field tuning on reaction step energetics and on the identity of the ground state allows us to propose refined design strategies for spin-allowed methane-to-methanol catalysis. We observe weak coupling of energetics and design principles between reaction steps (e.g., oxo formation vs methanol release), meaning that LFERs do not generalize across our larger catalyst set. To rationalize relative reactivity in known catalysts, we instead compute independent reaction energies and propose strategies for further improvements in catalyst design.

Regioselective Oxybromination of Benzene and Its Derivatives by Bromide Anion with a Mononuclear Nonheme Mn(IV)-Oxo Complex.

Oxybromination of aromatic compounds by high-valent metal-oxo intermediates has yet to be explored despite extensive studies on the oxybromination of aliphatic C-H bonds of hydrocarbons. Herein, we report the regioselective oxybromination of methoxy-substituted benzenes by a nonheme MnIV-oxo complex binding scandium ions, [(Bn-TPEN)MnIV(O)]2+-(Sc(OTf)3)2 (1), in the presence of tetrabutylammonium bromide. The regioselective oxybromination occurs at the carbon atom with the highest positive charge via electron transfer (ET) from the methoxy-substituted benzenes to 1. ET driving force dependence of the rate constants of ET from methoxy-substituted benzenes to 1 is well fitted in light of the Marcus theory of ET. Under photoirradiation, the oxybromination of benzene by 1 can be achieved via ET from benzene to the photoexcited state of 1, although no reaction occurs between benzene and the ground state of 1 in the dark. To the best of our knowledge, this is the first example of reporting the stoichiometric regioselective oxybromination of the benzene ring by a synthetic high-valent Mn(IV)-oxo complex and the catalytic regioselective oxybromination reaction with a Mn(II) complex and a terminal oxidant.

Importance of Entropic Contribution to Electrochemical Water Oxidation Catalysis

Electrochemical water oxidation is considered as one of the most important reactions for a sustainable future. However, in heterogeneous water oxidation, atomistic understanding of this four-electron reaction is still elusive. In particular, the mechanism of O–O bond formation, the coupled transfer of proton and electron, and the hopping of high-valent metal-oxo intermediates are challenging issues. To date, binding energy related descriptors have been used successfully to predict the catalytic activities by matching the experimental data and quantitatively comparing the performances. In this Perspective, we attempt to emphasize the significance of entropic contribution, like enthalpy, by highlighting recent literature and calculating the entropy from the available data. We envision that this Perspective can suggest a new research direction toward the catalyst design to control the entropy during water oxidation and be technologically useful for characterizing the temperature effects.

Activation of ferrate by carbon nanotube for enhanced degradation of bromophenols: Kinetics, products, and involvement of Fe(V)/Fe(IV)

Very recently, several studies have found that homogeneous reducing agents (e.g., sodium thiosulfate (Na2S2O3), and sodium sulfite (Na2SO3)) can activate ferrate to enhance the degradation of selected contaminants. In this work, it was found that heterogeneous carbon nanotube (CNT) could accelerate ferrate (Fe(VI)) for the degradation of bromophenols (BrPs) of environmental concerns and alleviate the appearance of undesired by-products in effluent. Fe(VI) could react with BrPs over a wide pH range of 6–10 with apparent second-order rate constants of 1.8–1850 M−1 s−1. Electrospray ionization-triple quadrupole mass spectrometry (ESI-QqQMS) analysis showed that dibrominated dihydroxylated biphenyls and dibrominated phenoxyphenols were possibly formed via coupling reaction of BrPs radicals generated from Fe(VI) oxidation through one-electron transfer. The presence of CNT could remarkably accelerate the degradation rates of BrPs by Fe(VI) in a wide pH range from 7 to 10. Moreover, the formed undesired polybrominated products during Fe(VI)/CNT oxidation were absorbed on CNT surface and thus removed from treated water. The Fe(VI)/CNT system was capable of selectively oxidizing electron-rich pollutants (e.g., BrPs, and sulfamethoxazole (SMX)), but reluctant to iopamidol (IPM) and nitrobenzene (NB). High-valent metal-oxo intermediates Fe(V)/Fe(IV) formed in situ from the reaction of CNT with Fe(VI) were likely responsible for this activation effect of CNT, which was further confirmed via using methyl phenyl sulfoxide (PMSO) as a probe compound. Comparatively, homogeneous reducing agent Na2S2O3 could enhance Fe(VI) degradation of BrPs at pH 7 and 8, while undesired polybrominated products were detected in effluent from Fe(VI)/Na2S2O3 system. These findings have crucial implications for the development of a promising oxidation process by combination of Fe(VI) and CNT for water and wastewater treatment.

Oxygen-Oxygen Bond Cleavage and Formation in Co(II)-Mediated Stoichiometric O2 Reduction via the Potential Intermediacy of a Co(IV) Oxyl Radical.

In reactions of significance to alternative energy schemes, metal catalysts are needed to overcome kinetically and thermodynamically difficult processes. Often, high-oxidation-state, high-energy metal oxo intermediates are proposed as mediators in elementary steps involving O-O bond cleavage and formation, but the mechanisms of these steps are difficult to study because of the fleeting nature of these species. Here we utilized a novel dianionic pentadentate ligand system that enabled a detailed mechanistic investigation of the protonation of a cobalt(III)-cobalt(III) peroxo dimer, a known intermediate in oxygen reduction catalysis to hydrogen peroxide. It was shown that double protonation occurs rapidly and leads to a low-energy O-O bond cleavage step that generates a Co(III) aquo complex and a highly reactive Co(IV) oxyl cation. The latter was probed computationally and experimentally implicated through chemical interception and isotope labeling experiments. In the absence of competing chemical reagents, it dimerizes and eliminates dioxygen in a step highly relevant to O-O bond formation in the oxygen evolution step in water oxidation. Thus, the study demonstrates both facile O-O bond cleavage and formation in the stoichiometric reduction of O2 to H2O with 2 equiv of Co(II) and suggests a new pathway for selective reduction of O2 to water via Co(III)-O-O-Co(III) peroxo intermediates.

Combined Multistate and Kohn-Sham Density Functional Theory Studies of the Elusive Mechanism of N-Dealkylation of N,N-Dimethylanilines Mediated by the Biomimetic Nonheme Oxidant FeIV(O)(N4Py)(ClO4)2.

The oxidative C-H bond activation mediated by heme and nonheme enzymes and related biomimetics is one of the most interesting processes in bioinorganic and oxidative chemistry. However, the mechanisms of these reactions are still elusive and controversy due to the involvement of highly reactive metal-oxo intermediates with multiple spin states, despite extensive experimental efforts, especially for the N-dealkylation of N,N-dialkyalinines. In this work, we employed multistate density functional theory (MSDFT) and the Kohn-Sham DFT to investigate the mechanism of N-demethylation of N,N-dimethyalinines oxidized by the reaction intermediate FeIV(O)(N4Py)(ClO4)2. The Kohn-Sham DFT study demonstrated that the reaction proceeds via a rate-limiting hydrogen atom transfer (HAT) step and a subsequent barrier-free oxygen rebound step to form the carbinol product. The MSDFT investigation on the first C-H activation further showed that this step is an initial hydrogen atom abstraction that is highly correlated between CEPT and HAT, i.e., both CEPT and HAT processes make significant contributions to the mechanism before reaching the diabatic crossing point, then the valence bond character of the adiabatic ground state is switched to the CEPT product configuration. The findings from this work may be applicable to other hydrogen abstraction process.

Relationship between Hydrogen-Atom Transfer Driving Force and Reaction Rates for an Oxomanganese(IV) Adduct.

Hydrogen atom transfer (HAT) reactions by high-valent metal-oxo intermediates are important in both biological and synthetic systems. While the HAT reactivity of FeIV-oxo adducts has been extensively investigated, studies of analogous MnIV-oxo systems are less common. There are several recent reports of MnIV-oxo complexes, supported by neutral pentadentate ligands, capable of cleaving strong C-H bonds at rates approaching those of analogous FeIV-oxo species. In this study, we provide a thorough analysis of the HAT reactivity of one of these MnIV-oxo complexes, [MnIV(O)(2pyN2Q)]2+, which is supported by an N5 ligand with equatorial pyridine and quinoline donors. This complex is able to oxidize the strong C-H bonds of cyclohexane with rates exceeding those of FeIV-oxo complexes with similar ligands. In the presence of excess oxidant (iodosobenzene), cyclohexane oxidation by [MnIV(O)(2pyN2Q)]2+ is catalytic, albeit with modest turnover numbers. Because the rate of cyclohexane oxidation by [MnIV(O)(2pyN2Q)]2+ was faster than that predicted by a previously published Bells-Evans-Polanyi correlation, we expanded the scope of this relationship by determining HAT reaction rates for substrates with bond dissociation energies spanning 20 kcal/mol. This extensive analysis showed the expected correlation between reaction rate and the strength of the substrate C-H bond, albeit with a shallow slope. The implications of this result with regard to MnIV-oxo and FeIV-oxo reactivity are discussed.

Bioinspired catalytic generation of high-valent cobalt-oxo species by the axially coordinated CoPc on pyridine-functionalized MWCNTs for the elimination of organic contaminants

Enzymes have always been a source of inspiration for the design and improvement of catalysts. Many examples are occurring in heme/non-heme metalloenzymes with the generation of active high-valent metal-oxo intermediates that are controlled by the surrounding amino acids/protein and axial residue ligands, facilitating the efficient oxidation of substrates in biochemical processes. Here, the high-valent cobalt-oxo species have been formed during the heterolysis of H2O2 activated by the bioinspired catalyst, axially coordinated cobalt phthalocyanine (CoPc) on pyridine-functionalized multi-walled carbon nanotubes (MWCNTs-Py), characterized by ultraviolet–visible and X-ray photoelectron spectroscopy. Formation process of the active cobalt-oxo species has been further confirmed by electrospray ionization mass spectrometry analysis and the results from the density functional theory (B3LYP/6-311G) calculations. Such high-valent cobalt-oxo species exhibit high reactivity and enough persistence for the oxidation of the target substrate, C.I. Acid Red 1. The oxidation products are nearly biodegradable small molecules identified by ultra-performance liquid chromatography/high-definition mass spectrometry. This strategy provides a foundation on developing efficient and persistent catalytic system, in particular oxidation processes based on the complex catalysts with N4 macrocycle structures.