Oxygen Atom Transfer Reactions Research Articles

Manganese-Mediated Electrochemical Oxidation of Thioethers to Sulfoxides Using Water as the Source of Oxygen Atoms.

Oxygen-atom transfer reactions are a prominent class of synthetic redox reactions that often use high-energy oxygen-atom donor reagents. Electrochemical methods can bypass these reagents by using water as the source of oxygen atoms through pathways involving direct or indirect (mediated) electrolysis. Here, manganese porphyrins and related mediators are shown to be effective molecular electrocatalysts for selective oxidation of thioethers to sulfoxides, without overoxidation to the sulfone. The reactions proceed by proton-coupled oxidation of a MnIII-OH2 species to generate a MnIV-OH and MnV═O species. This methodology is compared to direct electrolysis methods initiated by single-electron oxidation of the thioether, and chloride-mediated electrochemical oxidation of thioethers. The Mn-mediated reactions operate at lower applied potential and exhibit improved substrate scope and functional group compatibility relative to direct electrolysis, and the tunability of the Mn-based mediators allows for improved performance relative to chloride-mediated electrolysis. An electrochemical parallel screening platform is developed and applied to a library of pharmaceutically relevant thioethers.

Unraveling the Geometry-Driven C═C Epoxidation and C-H Hydroxylation Reactivity of Tetra-Coordinated Nonheme Iron(IV)-Oxo Complexes.

The electronic structure and reactivity of tetra-coordinated nonheme iron(IV)-oxo complexes have remained unexplored for years. The recent synthesis of a closed-shell iron(IV)-oxo complex [(quinisox)FeIV(O)]+ (1) has set up a platform to understand how such complexes compare with the celebrated open-shell iron-oxo chemistry. Herein, using density functional theory and ab initio calculations, we present an in-depth electronic structure investigation of the C═C epoxidation [oxygen atom transfer (OAT)] and C-H hydroxylation [hydrogen atom transfer (HAT)] reactivity of 1. Using a solvent-coordinated geometry of 1 (1') and other potential tetra-coordinated iron(IV)-oxo complexes bearing rigid ligands (2 and 3), we established the geometric origin of spin-state energetics and reactivity of 1. Complex 1 featuring a strong Fe-O bond exhibits OAT and HAT reactivity in its quintet state. The lowest quintet OAT pathway has a lower barrier by ∼4 kcal/mol than the quintet HAT pathway, corroborating the experimentally observed gas-phase OAT reactivity preference. A conventional HAT reactivity preference for 2 and a comparable OAT and HAT reactivity for 3 are observed. This further supports the geometry-driven reactivity preference for 1. Noncovalent interaction analyses reveal a pronounced π-π interaction between the substrate and ligand in the OAT transition state, rationalizing the origin of the observed reactivity preference for 1.

Photo-assisted selective oxidation of monoterpenes by a covalently supported dioxo-molybdenum complex on TiO2: Effect of electron donor ligands

High-valent dioxo-Mo species have demonstrated the ability to catalyze industrially interesting alkene-to-epoxide transformations via oxygen atom transfer (OAT) reactions. The impact of electron donor ligands of dioxo-molybdenum complexes [MoO2Ln] covalently supported on TiO2 nanotubes (MoO2Ln/TiO2NT) on OAT to α-pinene, β-pinene, (R)-limonene and camphene has been investigated through the use of UV–vis radiation and molecular oxygen. Molybdenum complexes with electron donor ligands, such as bipyridine, bispyrazole, and terpyridine, exhibited high conversion and selectivity towards epoxide formation. This suggests that electron donation enhances the efficiency of photostimulated OAT. The photonic efficiency (ξ) demonstrates a linear correlation between the ligand structure and the OAT activity, indicating that the electron donation of the ligands enhances electron mobility towards the Mo=O bond. This correlation is evident in the position of the IR and Raman νsym(O=Mo=O) and vasym(O=Mo=O) vibrations of the complex Mo.

Identification, Characterization, and Electronic Structures of Interconvertible Cobalt-Oxygen TAML Intermediates.

The reaction of Li[(TAML)CoIII]·3H2O (TAML = tetraamido macrocyclic tetraanionic ligand) with iodosylbenzene at 253 K in acetone in the presence of redox-innocent metal ions (Sc(OTf)3 and Y(OTf)3) or triflic acid affords a blue species 1, which is converted reversibly to a green species 2 upon cooling to 193 K. The electronic structures of 1 and 2 have been determined by combining advanced spectroscopic techniques (X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), X-ray absorption spectroscopy/extended X-ray absorption fine structure (XAS/EXAFS), and magnetic circular dichroism (MCD)) with ab initio theoretical studies. Complex 1 is best represented as an S = 1/2 [(Sol)(TAML•+)CoIII---OH(LA)]- species (LA = Lewis/Brønsted acid and Sol = solvent), where an S = 1 Co(III) center is antiferromagnetically coupled to S = 1/2 TAML•+, which represents a one-electron oxidized TAML ligand. In contrast, complex 2, also with an S = 1/2 ground state, is found to be multiconfigurational with contributions of both the resonance forms [(H-TAML)CoIV═O(LA)]- and [(H-TAML•+)CoIII═O(LA)]-; H-TAML and H-TAML•+ represent the protonated forms of TAML and TAML•+ ligands, respectively. Thus, the interconversion of 1 and 2 is associated with a LA-associated tautomerization event, whereby H+ shifts from the terminal -OH group to TAML•+ with the concomitant formation of a terminal cobalt-oxo species possessing both singlet (SCo = 0) Co(III) and doublet (SCo = 1/2) Co(IV) characters. The reactivities of 1 and 2 at different temperatures have been investigated in oxygen atom transfer (OAT) and hydrogen atom transfer (HAT) reactions to compare the activation enthalpies and entropies of 1 and 2.

Bioinspired axial S-coordinated single-atom cobalt catalyst to efficient activate peroxymonosulfate for selective high-valent Co-Oxo species generation

The efficient activation and selective high-valent metal-oxo (HVMO) species generation remain challenging for peroxymonosulfate (PMS)-based advanced oxidation processes (PMS-AOPs) in water purification. The underlying mechanism of the activation pathway is ambiguous, leading to a massive dilemma in the control and regulation of HVMO species generation. Herein, bioinspired by the bio-oxidase structure of cytochrome P450, the axial coordination strategy was adopted to tailor a single-atom cobalt catalyst (CoN4S-CB) with an axial S coordination. CoN4S-CB high-selectively generated high-valent Co-Oxo species (Co(IV)=O) via PMS activation. Co(IV)=O demonstrated an ingenious oxygen atom transfer (OAT) reaction to achieve the efficient degradation of sulfamethoxazole (SMX), and this allowed robust operation in various complex environments. The axial S coordination modulated the 3d orbital electron distribution of the Co atom. Density functional theory (DFT) calculation revealed that the axial S coordination decreased the energy barrier for PMS desorption and lowered the free energy change (ΔG) for Co(IV)=O generation. CoN4S-PMS* had a narrow d-band close to the Fermi level, which enhanced charge transfer to accelerate the cleavage of O-O and O-H bonds in PMS. This work provides a broader perspective on the activator design with natural enzyme structure-like active sites to efficient activate PMS for selective HVMO species generation.

From Criegee to Breslow: How π-Donors Steer the Route of Olefin Ozonolysis.

While π-bonds typically undergo cycloaddition with ozone, resulting in the release of much-noticed carbonyl O-oxide Criegee intermediates, lone-pairs of electrons tend to selectively accept a single oxygen atom from O3, producing singlet dioxygen. We questioned whether the introduction of potent electron-donating groups, akin to N-heterocyclic olefins, could influence the reactivity of double bonds - shifting from cycloaddition to oxygen atom transfer or generating lesser-known, yet stabilized, donor-substituted Criegee intermediates. Consequently, we conducted a comparative computational study using density functional theory on a series of model olefins with increasing polarity due to (asymmetric) π-donor substitution. Reaction path computations indicate that highly polarized double bonds, instead of forming primary ozonides in their reaction with O3, exhibit a preference for accepting a single oxygen atom, resulting in a zwitterionic species formally identified as a carbene-carbonyl adduct. This previously unexplored reactivity potentially introduces aldehyde umpolung chemistry (Breslow intermediate) through olefin ozonolysis. Considering solvent effects implicitly reveals that increased solvent polarity further directs the trajectories toward a single oxygen atom transfer reactivity by stabilizing the zwitterionic character of the transition state. The competing modes of chemical reactivity can be explained by a bifurcation of the reaction valley in the post-transition state region.

Probing tungsten-alkylidyne cyclic polymer initiator decomposition pathways with oxidants

An OCO-pincer supported tungsten(VI) alkylidyne exhibits diverse reactivity depending on the identity of the oxidizing agent and the stoichiometry of the reaction. Oxidation reactions are studied with azo, nitroso, and oxo compounds. Benzo(c)cinnoline facilitates migratory insertion of the alkylidyne carbon in the pincer backbone forming a tethered tungsten (VI) alkylidene complex. Analogous azobenzene activates a CC bond in the tert—butyl group of the alkylidyne and results in a tungsten di-imido complex. Nitrosobenzene and pyridine N-oxide undergo oxygen atom transfer (OAT) reactions and result in tungsten oxo complexes. Reactions with nitrosobenzene are sensitive to stoichiometry; CC bond activation is observed in stoichiometric reactions, while only OAT occurs with excess nitrosobenzene.

Enhanced Reactivity through Equatorial Sulfur Coordination in Nonheme Iron(IV)-Oxo Complexes: Insights from Experiment and Theory.

Sulfur ligation in metalloenzymes often gives the active site unique properties, whether it is the axial cysteinate ligand in the cytochrome P450s or the equatorial sulfur/thiol ligation in nonheme iron enzymes. To understand sulfur ligation to iron complexes and how it affects the structural, spectroscopic, and intrinsic properties of the active species and the catalysis of substrates, we pursued a systematic study and compared sulfur with amine-ligated iron(IV)-oxo complexes. We synthesized and characterized a biomimetic N4S-ligated iron(IV)-oxo complex and compared the obtained results with an analogous N5-ligated iron(IV)-oxo complex. Our work shows that the amine for sulfur replacement in the equatorial ligand framework leads to a rate enhancement for oxygen atom and hydrogen atom transfer reactions. Moreover, the sulfur-ligated iron(IV)-oxo complex reacts through a different reaction mechanism as compared to the N5-ligated iron(IV)-oxo complex, where the former reacts through hydride transfer with the latter reacting via radical pathways. We show that the reactivity differences are caused by a dramatic change in redox potential between the two complexes. Our studies highlight the importance of implementing a sulfur ligand into the equatorial ligand framework of nonheme iron(IV)-oxo complexes and how it affects the physicochemical properties of the oxidant and its reactivity.

Enhanced Reactivities of Iron(IV)-Oxo Porphyrin Species in Oxidation Reactions Promoted by Intramolecular Hydrogen-Bonding.

High-valent iron-oxo species are one of the common intermediates in both biological and biomimetic catalytic oxidation reactions. Recently, hydrogen-bonding (H-bonding) has been proved to be critical in determining the selectivity and reactivity. However, few examples have been established for mechanistic insights into the H-bonding effect. Moreover, intramolecular H-bonding effect on both C-H activation and oxygen atom transfer (OAT) reactions in synthetic porphyrin model system has not been investigated yet. In this study, a series of heme-containing iron(IV)-oxo porphyrin species with or without intramolecular H-bonding are synthesized and characterized. Kinetic studies revealed that intramolecular H-bonding can significantly enhance the reactivity of iron(IV)-oxo species in OAT, C-H activation, and electron-transfer reactions. This unprecedented unified H-bonding effect is elucidated by theoretical calculations, which showed that intramolecular H-bonding interactions lower the energy of the anti-bonding orbital of iron(IV)-oxo porphyrin species, resulting in the enhanced reactivities in oxidation reactions irrespective of the reaction type. To the best of the knowledge, this is the first extensive investigation on the intramolecular H-bonding effect in heme system. The results show that H-bonding interactions have a unified effect with iron(IV)-oxo porphyrin species in all three investigated reactions.

A tale of two topological isomers: Uptuning [FeIV(O)(Me4cyclam)]2+ for olefin epoxidation

TMC-anti and TMC-syn, the two topological isomers of [FeIV(O)(TMC)(CH3CN)]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, or Me4cyclam), differ in the orientations of their FeIV=O units relative to the four methyl groups of the TMC ligand framework. The FeIV=O unit of TMC-anti points away from the four methyl groups, while that of TMC-syn is surrounded by the methyl groups, resulting in differences in their oxidative reactivities. TMC-syn reacts with HAT (hydrogen atom transfer) substrates at 1.3- to 3-fold faster rates than TMC-anti, but the reactivity difference increases dramatically in oxygen-atom transfer reactions. R2S substrates are oxidized into R2S=O products at rates 2-to-3 orders of magnitude faster by TMC-syn than TMC-anti. Even more remarkably, TMC-syn epoxidizes all the olefin substrates in this study, while TMC-anti reacts only with cis-cyclooctene but at a 100-fold slower rate. Comprehensive quantum chemical calculations have uncovered the key factors governing such reactivity differences found between these two topological isomers.

Mechanistic study on MeReVO(edt)Im catalysis for the oxygen atom transfer from pyridine oxide to Ph3As: Kinetics and computational study

The oxorhenium(V) monomer (CH3Re(V)O(edt)(Im) (where edt = 1,2 ethanedithiolate, Im= Imidazole) catalyzes the oxygen atom transfer reaction from pyridine N-oxide and substituted pyridine N-oxide to triphenylarsine (Ph3As). The kinetic results have shown that the reaction rate is first order with respect to the catalyst and pyridine N-oxide concentrations, and first order with respect to [Ph3As] at low concentration and zero order at high [Ph3As]. Also, the reaction is zero order with respect to the imidazole concentration. Therefore, rate law is R = k [Re-Im] [PyNO][Ph3As] at low Ph3As concentration and the rate law is R = k [Re-Im] [PyNO] at high Ph3As concentration. The electronic effect of the oxidant was investigated by studying the reaction rate constants of different substituted pyridine NOxide. The correlation of the rate constant values with σ is linear with reaction constant ρ = -2.4. A negative value indicates that the rate increases with electron-donating substituents. The effect of electron donor substituent on the reaction rate is mainly due to the enhancement of the binding of pyridine N-oxide to the ReVO in the first step of the proposed mechanism. The oxidation of ReVO to ReVIIO2 and release of the pyridine step is not highly sensitive to the nature of the substituent on the pyridine. The computational study indicates that the oxidation of ReVO to ReVIIO2 and release of the pyridine step is insensitive to the nature of the substituent on the pyridine with the average estimated activation barrier ≈ 9 kcal/mol and its less than the estimated activation barrier in the absence of imidazole (≈ 11.5 kcal/mol). This result support that the imidazole act as nucleophile to assist the oxidation of ReVO to ReVIIO2 step.

Synthesis, Structure and Reactivity of a Mononuclear N,N,O-Bound Fe(II) α-Keto-Acid Complex.

A bulky, tridentate phenolate ligand (ImPh2 NNOtBu ) was used to synthesise the first example of a mononuclear, facial, N,N,O-bound iron(II) benzoylformate complex, [Fe(ImPh2 NNOtBu )(BF)] (2). The X-ray crystal structure of 2 reveals that the iron centre is pentacoordinate (τ=0.5), with a vacant site located cis to the bidentate BF ligand. The Mössbauer parameters of 2 are consistent with high-spin iron(II), and are very close to those reported for α-ketoglutarate-bound non-heme iron enzyme active sites. According to NMR and UV-vis spectroscopies, the structural integrity of 2 is retained in both coordinating and non-coordinating solvents. Cyclic voltammetry studies show that the iron centre has a very low oxidation potential and is more prone to electrochemical oxidation than the redox-active phenolate ligand. Complex 2 reacts with NO to form a S=3 /2 {FeNO}7 adduct in which NO binds directly to the iron centre, according to EPR, UV-vis, IR spectroscopies and DFT analysis. Upon O2 exposure, 2 undergoes oxidative decarboxylation to form a diiron(III) benzoate complex, [Fe2 (ImPh2 NNOtBu )2 (μ2 -OBz)(μ2 -OH)2 ]+ (3). A small amount of hydroxylated ligand was also observed by ESI-MS, hinting at the formation of a high-valent iron(IV)-oxo intermediate. Initial reactivity studies show that 2 is capable of oxygen atom transfer reactivity with O2 , converting methyl(p-tolyl)sulfide to sulfoxide.

Mechanistic insights on the epoxidation of alkenes by high-valent non-heme Fe(iv) and Fe(v) oxidants: a comparative theoretical study

This work is based on the screening of better high-valent oxidants, and also includes a mechanistic study during oxygen atom transfer reactions.

Ta+ and Nb+ + CO2: intersystem crossing in ion-molecule reactions.

The reactions of Ta+ and Nb+ with CO2 proceed only by a highly efficient oxygen atom transfer reaction to the respective oxide at room temperature in the gas phase. Although the product spin states are not determined, thermochemistry dictates that they must be different from ground state quintet Ta+ and Nb+, implying that intersystem crossing (ISC) has occurred. Recent reactive scattering experiments found dominant indirect dynamics for the reaction with Ta+ hinting at a bottleneck along the reaction path. The question on the nature of the bottleneck, whether it involves a crossing point or a transition state, could not be finally answered because theory located both close to each other. Here, we aim at shedding further light onto the impact of intersystem crossing on the reaction dynamics and ultimately the reactivity of transition metal ion reactions in the gas phase. We employ a combination of thermal kinetics for Ta+ and Nb+ with CO2 using a selected-ion flow tube (SIFT) apparatus and differential scattering cross sections for Nb+ + CO2 from crossed-beam velocity map imaging. The reaction with niobium again shows dominant indirect dynamics and in general very similar dynamics compared to Ta+ + CO2. At thermal energies, both reactions show sub-collisional rate constants with small negative temperature dependencies. Experiments are complemented by high level quantum chemical calculations of the minimum energy pathway. Statistical modelling well-reproduces the experimental thermal rate constants, and suggests that the Nb+ reaction is rate-limited by the intersystem crossing at thermal energies.

Influence of Equatorial Co-Ligands on the Reactivity of LFeIIIOIPh.

Previous biomimetic studies clearly proved that equatorial ligands significantly influence the redox potential and thus the stability/reactivity of biologically important oxoiron intermediates; however, no such studies were performed on FeIIIOIPh species. In this study, the influence of substituted pyridine co-ligands on the reactivity of iron(III)-iodosylbenzene adduct has been investigated in sulfoxidation and epoxidation reactions. Selective oxidation of thioanisole, cis-cyclooctene, and cis- and trans-stilbene in the presence of a catalytic amount of [FeII(PBI)3](OTf)2 with PhI(OAc)2 provide products in good to excellent yields through an FeIIIOIPh intermediate depending on the co-ligand (4R-Py) used. Several mechanistic studies were performed to gain more insight into the mechanism of oxygen atom transfer (OAT) reactions to support the reactive intermediate and investigate the effect of the equatorial co-ligands. Based on competitive experiments, including a linear free-energy relationship between the relative reaction rates (logkrel) and the σp (4R-Py) parameters, strong evidence has been observed for the electrophilic character of the reactive species. The presence of the [(PBI)2(4R-Py)FeIIIOIPh]3+ intermediates and the effect of the co-ligands was also supported by UV-visible measurements, including the color change from red to green and the hypsochromic shifts in the presence of co-ligands. This is another indication that the title iron(III)-iodosylbenzene adduct is able to oxygenate sulfides and alkenes before it is transformed into the oxoiron form by cleavage of the O-I bond.

Unravelling the Effect of Acid-Driven Electron Transfer in High-Valent FeIV =O/MnIV =O Species and Its Implications for Reactivity.

The electron transfer (ET) step is one of the crucial processes in biochemical redox reactions that occur in nature and has been established as a key step in dictating the reactivity of high-valent metal-oxo species. Although metalloenzymes possessing metal-oxo units at their active site are typically associated with outer-sphere electron transfer (OSET) processes, biomimetic models, in contrast, have been found to manifest either an inner-sphere electron transfer (ISET) or OSET mechanism. This distinction is clearly illustrated through the behaviour of [(N4Py)MnIV (O)]2+ (1) and [(N4Py)FeIV (O)]2+ (2) complexes, where complex 1 showcases an OSET mechanism, while complex 2 exhibits an ISET mechanism, especially evident in their reactions involving C-H bond activation and oxygen atom transfer reactions in the presence of a Lewis/Bronsted acid. However, the precise reason for this puzzling difference remains elusive. This work unveils the origin of the perplexing inner-sphere vs outer-sphere electron transfer process (ISET vs OSET) in [(N4Py)MnIV (O)]2+ (1) and [(N4Py)FeIV (O)]2+ (2) species in the presence of Bronsted acid. The calculations indicate that when the substrate (toluene) approaches both 1 and 2 that is hydrogen bonded with two HOTf molecules (denoted as 1-HOTf and 2-HOTf, respectively), proton transfer from one of the HOTf molecules to the metal-oxo unit is triggered and a simultaneous electron transfer occurs from toluene to the metal centre. Interestingly, the preference for OSET by 1-HOTf is found to originate from the choice of MnIV =O centre to abstract spin-down (β) electron from toluene to its δ(dxy ) orbital. On the other hand, in 2-HOTf, a spin state inversion from triplet to quintet state takes place during the proton (from HOTf) coupled electron transfer (from toluene) preferring a spin-up (α) electron abstraction to its σ* (dz 2 ) orbital mediated by HOTf giving rise to ISET. In addition, 2-HOTf was calculated to possess a larger reorganisation energy, which facilitates the ISET process via the acid. The absence of spin-inversion and smaller reorganisation energy switch the mechanism to OSET for 1-HOTf. Therefore, for the first time, the significance of spin-state and spin-inversion in the electron transfer process has been identified and demonstrated within the realm of high-valent metal-oxo chemistry. This discovery holds implications for the potential involvement of high-valent Mn-oxo species in performing similar transformative processes within Photosystem II.

Enhancement of Reactivity of a RuIV-Oxo Complex in Oxygen-Atom-Transfer Catalysis by Hydrogen-Bonding with Amide Moieties in the Second Coordination Sphere.

We have synthesized and characterized a RuII-OH2 complex (2), which has a pentadentate ligand with two pivalamide groups as bulky hydrogen-bonding (HB) moieties in the second coordination sphere (SCS). Complex 2 exhibits a coordination equilibrium through the coordination of one of the pivalamide oxygens to the Ru center in water, affording a η6-coordinated complex, 3. A detailed thermodynamic analysis of the coordination equilibrium revealed that the formation of 3 from 2 is entropy-driven owing to the dissociation of the axial aqua ligand in 2. Complex 2 was oxidized by a CeIV salt to produce the corresponding RuIII(OH) complex (5), which was characterized crystallographically. In the crystal structure of 5, hydrogen bonds are formed among the NH groups of the pivalamide moieties and the oxygen atom of the hydroxo ligand. Further 1e--oxidation of 5 yields the corresponding RuIV(O) complex, 6, which has intramolecular HB of the oxo ligand with two amide N-H protons. Additionally, the RuIII(OH) complex, 5, exhibits disproportionation to the corresponding RuIV(O) complex, 6, and a mixture of the RuII complexes, 2 and 3, in an acidic aqueous solution. We investigated the oxidation of a phenol derivative using complex 6 as the active species and clarified the switch of the reaction mechanism from hydrogen-atom transfer at pH 2.5 to electron transfer, followed by proton transfer at pH 1.0. Additionally, the intramolecular HB in 6 exerts enhancing effects on oxygen-atom transfer reactions from 6 to alkenes such as cyclohexene and its water-soluble derivative to afford the corresponding epoxides, relative to the corresponding RuIV(O) complex (6') lacking the HB moieties in the SCS.

Wireless Electrochemical Reactor for Accelerated Exploratory Study of Electroorganic Synthesis.

Electrosynthesis is an emerging tool to construct value-added fine chemicals under mild and sustainable conditions. However, the complex apparatus required impedes the facile development of new electrochemistry in the laboratory. Herein, we proposed and demonstrated the concept of wireless electrochemistry (Wi-eChem) based on wireless power transfer technology. The core of this concept is the dual-function wireless electrochemical magnetic stirrer that provides an electrolysis driving force and mixing simultaneously in a miniaturized form factor. This Wi-eChem system allowed electrochemists to execute electrochemical reactions in a manner similar to traditional organic chemistry without handling wire connections. The controllability, reusability, and versatility were validated with a series of modern electrosynthesis reactions, including electrodecarboxylative etherification, electroreductive olefin-ketone coupling, and electrochemical nickel-catalyzed oxygen atom transfer reaction. Its remarkably simplified operation enabled its facile integration into a fully automated robotic synthesis platform to achieve autonomous parallel electrosynthesis screening.

How Ligand Geometry Affects the Reactivity of Co(II) Cyclam Complexes

AbstractCobalt complexes are extensively studied as bioinspired models for non‐heme oxygenases as they facilitate both the stabilization and characterization of metal‐oxygen intermediates. As an analog to the well‐known Co(cyclam) complex Co{N4} (cyclam=1,4,8,11‐tetraazacyclotetradecane), the CoII complex Co{i‐N4} with the isomeric isocyclam ligand (isocyclam=1,4,7,11‐tetraazacyclotetradecane) was synthesized and characterized. Despite the identical N4 donor set of both complexes, Co{i‐N4} enables the 2e−/2H+ reduction of O2 with a lower overpotential (ηeff of 385 mV vs. 540 mV for Co{N4}), albeit with a diminished turnover frequency. Characterization of the intermediates formed upon O2 activation of Co{i‐N4} reveals a structurally identified stable μ‐peroxo CoIII dimer as the main product. A superoxo CoIII species is also formed as a minor product, as indicated by EPR spectroscopy. In further reactivity studies, the electrophilicity of these in situ generated Co−O2 species was demonstrated by the oxidation of the O−H bond of TEMPO−H (2,2,6,6‐tetramethylpiperidin‐1‐ol) via a H atom abstraction process. Unlike the known Co(cyclam), Co{i‐N4} can be employed in oxygen atom transfer reactions oxidizing triphenylphosphine to the corresponding phosphine oxide highlighting the impact of geometrical modifications of the ligand while preserving the ring size and donor atom set on the reactivity of biomimetic oxygen activating complexes.

Photoinduced Oxygen Atom Transfer to α‐Pinene and R‐Carvone using a Dioxo‐Molybdenum (VI) Complex Incorporated within a Modified UiO‐67 (Zr/Ti) MOF

AbstractWe report a highly selective (100 %) epoxidation of α‐pinene and R‐carvone using an oxygen atom transfer (OAT) reaction facilitated by a dioxo‐Mo complex (Mo(VI)O2Cl2Ln) incorporated into the ligand 5,5’‐dicarboxylate‐2,2’‐bipyridine (bpydc) within a Metal‐Organic Framework (MOF) type UiO‐67. Photo‐stimulated (350 nm) OAT reaction was carried out with oxygen molecular used as the oxidant for 10 h. UiO‐67 was synthesized with a mixture of the ligands 2,2′‐biphenyl‐5,5′‐dicarboxylate (bpdc) and 2,2‐bipyridine‐5,5‐dicarboxylate (bpydc) in different molar ratios (67 : 33, 50 : 50, 70 : 30, 0 : 100 bpdc : bpydc) to promote a higher presence of catalytic sites, i. e., the dioxo‐Mo complex units. Furthermore, a post‐synthetic exchange of Zr for Ti, between 64 : 36 to 78 : 22 Ti : Zr molar ratio, was performed to improve the optical properties of the MOF and promote the photoinduced OAT reaction. The Catalytic system was characterized by FTIR, XRD, 1H NMR, XPS, TGA, N2 adsorption/desorption and UV‐Vis‐DR. The amount of the epoxide monoterpene is proportional to the number of the dioxomolybdenum(VI) units (MoO2) incorporated in the UiO‐67 (Zr/Ti), and the OAT reaction selectivity is due to the absence of the oxygen radicals in the medium of reaction. Besides, The Mo complex exhibited excellent stability after five cycles of use.