Molecular Dioxygen Research Articles

Exceptional Substrate Diversity in Oxygenation Reactions Catalyzed by a Bis(μ-oxo) Copper Complex.

The enzyme tyrosinase contains a reactive side‐on peroxo dicopper(II) center as catalytically active species in C−H oxygenation reactions. The tyrosinase activity of the isomeric bis(μ‐oxo) dicopper(III) form has been discussed controversially. The synthesis of bis(μ‐oxo) dicopper(III) species [Cu2(μ‐O)2(L1)2](X)2 ([O1](X)2, X=PF6 − , BF4 −, OTf−, ClO4 −), stabilized by the new hybrid guanidine ligand 2‐{2‐((dimethylamino)methyl)phenyl}‐1,1,3,3‐tetramethylguanidine (L1), and its characterization by UV/Vis, Raman, and XAS spectroscopy, as well as cryo‐UHR‐ESI mass spectrometry, is described. We highlight selective oxygenation of a plethora of phenolic substrates mediated by [O1](PF6)2, which results in mono‐ and bicyclic quinones and provides an attractive strategy for designing new phenazines. The selectivity is predicted by using the Fukui function, which is hereby introduced into tyrosinase model chemistry. Our bioinspired catalysis harnesses molecular dioxygen for organic transformations and achieves a substrate diversity reaching far beyond the scope of the enzyme.

Chemical and Biochemical Reactions of Aromatic Furazan Compounds

Aromatic furazan has numerous pharmacologic and industrial applications. As part of our work on aromatic furazan chemistry and biochemistry, benzofurazan N-oxides, on irradiation using a high-pressure mercury lamp with a Pyrex filter in acetonitrile containing a little water, afforded 1H-azepine-2,7-dione. Mechanistic studies on the photoreaction using a low-pressure mercury lamp and photosensitizer suggest that photosensitized formation of 1H-azepine-2,7-dione with the aromatic hydrocarbon may be carried out by reabsorption of fluorescence. Quinoxaline 1,4-dioxide, phenazine 5,10-dioxide, and pyrido[2,3-b]pyrazine derivatives were synthesized from the corresponding aromatic or heteroaromatic furazan N-oxides by silica gel or molecular sieves under solvent-free conditions using microwave irradiation. The toxicities of some benzofurazans were examined on Escherichia coli; these may due to their reduction within the E. coli cell and their reoxidization by molecular dioxygen to form superoxide and hydrogen peroxide. The formation of 4,7-dicyanobenzofurazan anion radical in the E. coli cell suspension-4,7-dicyanobenzofurazan-glucose system in the absence of O2 was followed by ESR spectroscopy. 4,7-Dimethylbenzofurazan was transformed by 1O2 produced by irradiation of C60 into 4,7-dimethylbenzofurazan 4,7-endoperoxide. The endoperoxide decomposed back to 4,7-dimethylbenzofurazan at room temperature. 4,7-Dimethylbenzofurazan was transformed by irradiation with the third harmonic of a Quanta-Ray Nd:YAG laser (355 nm) into (2Z,4Z)-2,5-dimethylhexa-2,4-dienedinitrile monoxide. Irradiation of 4,7-dimethylbenzofurazan yielded a photoproduct with a quantum yield 0.48 and chemical yield 99%.

Solvent Dependent Divergent Reactivity of Electron‐Rich Dienones with and without Visible Light: Access to Cyclopropanated Furans and Butenolides

AbstractVisible light excitation of electron‐rich dienones in isopropanol solvent under ambient conditions using hexafluoroisopropanol (HFIP) as an additive promotes intramolecular radical cascade cyclization to afford cyclopropanated furans. Molecular dioxygen in the air serves as a redox catalyst in this reaction which is proposed to proceed through a radical cation intermediate generated by single‐electron transfer (SET) from a phototransient dienone to oxygen. By changing the solvent from isopropanol to HFIP, exclusive formation of substituted butenolides occurs via ionic cascade cyclization involving E→Z isomerization/lactonization/thiolate addition. HFIP is assumed to act as a medium, hydrogen bond donor catalyst, and a Lewis acid substitute as well. This reaction may be conducted even in the absence of light and no catalyst or reagent is required.magnified image

Catalytic aerobic radical polymerization in typical redox-non-innocent solvents as potential low-efficiency initiators

Certain complexes of some transition metal cations in the high oxidation state could oxidize some organic substrates with labile C-H moieties, leading to the corresponding cations in the lower" oxidation state and some carbon-centered radicals. The former would form oxidative complexes with molecular dioxygen to continuously oxidize organic substrates, while the latter would initiate polymerization of vinylic monomers. Such catalytic oxidation is adopted to initiate radical polymerization of methyl methacrylate (MMA) and styrene (St) with cyclohexanone (CyHO) and benzylic hydrocarbons as both the solvent and the substrate. Although, a large array of complexes could trigger the polymerization, CuII/2,2′-bipyridine complexes display a maximum turnover frequency above 200 h–1 during the catalytic aerobic radical polymerization of MMA in CyHO at 70–80 °C, but only less than 0.4% of CyHO is involved in chain formatting. CuII/ligand-catalyzed aerobic radical polymerization of St in CyHO exhibit comparable behaviors. Only CoII complexes could catalyze the aerobic radical polymerization of MMA in para-xylene and cumene at 90 °C, but only 0.1% of PX and 0.3% of cumene are involved in chain forming.

Peroxo-Cerium(IV)-Containing Polyoxometalates: [CeIV6(O2)9(GeW10O37)3]24-, a Recyclable Homogeneous Oxidation Catalyst.

The class of peroxo-cerium-containing polyoxometalates has been discovered via the synthesis of the 9-peroxo-6-cerium(IV)-containing 30-tungsto-3-germanate, [CeIV6(O2)9(GeW10O37)3]24- (1). Polyanion 1 consists of a cyclic [Ce6(O2)9]6+ assembly that is stabilized by three dilacunary [GeW10O37]10- Keggin fragments. The title polyanion 1 is solution-stable, on the basis of 183W nuclear magnetic resonance, and was shown to act as a recyclable homogeneous catalyst for the selective, microwave-activated sulfoxidation of the model substrate methionine to the sulfoxide in the absence and to the sulfone in the presence of hydrogen peroxide. Solution and solid-state Raman as well as solid-state infrared studies of 1 demonstrated the complete loss (and regain) of the nine peroxo groups in situ during the catalytic cycle, suggesting that the peroxo-free {Ce6(GeW10)3} skeleton remains most likely intact during the catalytic cycle. Solid-state X-ray photoelectron spectroscopy measurements showed that peroxo loss is accompanied by reduction of the cerium ions from +4 to +3, which is fully reversible. Density functional theory calculations are in complete agreement with all of these observations and furthermore suggest that the reduction of the six cerium(IV) ions is accompanied by the formation of molecular dioxygen.

Big Time

The Proterozoic Eon was once regarded as the neglected middle half of Earth history. The name refers to early animals, but they did not appear until the eon (2.5–0.54 Ga) was nearly over. Eukaryotic cells and sexual reproduction evolved much earlier in the eon, as did chloroplasts. Molecular dioxygen, the presence of which altered the geochemical behavior of nearly every element essential to life, rose from negligible to near-modern levels, and then plummeted before rising fitfully again. Plate tectonics took on a modern form, and two supercontinents, Nuna and Rodinia, successively congregated and later dispersed. Climate regulatory failures, i.e., Snowball Earth, appear to be a uniquely Proterozoic phenomenon, having occurred twice in rapid succession near the end of the eon (from 717 to 660 Ma and from 650 to 635 Ma) and arguably once near its beginning (ca. 2.43 Ga). Dynamic sea glaciers covered Snowball Earth oceans from pole to pole, and equatorial sublimation drove slow-moving ice sheets on land. Ultimately, the gradual accumulation of CO2 triggered rapid deglaciation and transient greenhouse aftermaths. Physically based and geologically tested, Neoproterozoic Snowball Earth appears to have molecular legacies in ancient bitumens and modern organisms. This is the story of my love affair with an eon that is now a little less neglected.

Stabilizing Terminal Ni(III)–Hydroxide Complex Using NNN-Pincer Ligands: Synthesis and Characterization

The reaction of [Ni(COD)2] (COD; cyclooctadiene) in THF with the NNN-pincer ligand bis(imino)pyridyl (L1) reveals a susceptibility to oxidation in an inert atmosphere ([O2] level <0.5 ppm), resulting in a transient Ni:dioxygen adduct. This reactive intermediate abstracts a hydrogen atom from THF and stabilizes an uncommon Ni(III) complex. The complex is crystallographically characterized by a molecular formula of [NiIII(L1··)2-(OH)] (1). Various isotopically labeled experiments (16O/18O) assertively endorse the origin of terminal oxygen based ligand in 1 due to the activation of molecular dioxygen. The presence of proton bound to the terminal oxygen in 1 is well supported by NMR, IR spectroscopy, DFT calculations, and hydrogen atom transfer (HAT) reactions promoted by 1. The observation of shakeup satellite peaks for the primary photoelectron lines of Ni(2p) in the X-ray photoelectron spectroscopy (XPS) unambiguously confirms the paramagnetic signature associated with the distorted square planar nickel ion, which is consistent with the trivalent oxidation state assigned for the nickel ion in 1. The variable temperature magnetic susceptibility data of 1 shows dominant antiferromagnetic interactions exist among the paramagnetic centers, resulting in an overall S = 1/2 ground state. Variable temperature X-band EPR studies performed on 1 show evidence for the S = 1/2 ground state, which is consistent with magnetic data. The unusual g-tensor extracted for the ground state S = 1/2 is analyzed under a strong exchange limit of spin-coupled centers. The electronic structure predicted for 1 is in good agreement with theoretical calculations.

An experimental test for the mass independent isotopic fractionation mechanism proposed for ozone

Ozone exhibits large and mass independent isotopic fractionations (MIF) in oxygen isotope ratios relative to molecular di-oxygen (O2) from which it is formed. An interpretation of this effect was proposed based on the behavior of the indistinguishable isotopes 16O in scattering processes. We report here an experiment aimed at testing one of the predictions of this model.O3 was formed by high frequency discharge in O2 with pressures ranging between 1.6 and 38 Torr. The isotopic evolution of the closed O2 reservoir was monitored during its distillation taking place during the continuous removal of ozone by condensation. Its composition evolves from a mass independent to a mass dependent fractionation along with the decrease in pressure. The isotopic pathways defined by this evolution in the 3 isotopes diagram are in quantitative agreement with the theoretical prediction of the disappearance of MIF with the increase of the complex lifetime stabilized as ozone.

Selective activation of C[sbnd]H bond into C[dbnd]O bond of phenols in para-position via aerobic oxidation

An efficient method for the oxidation of phenols to 1,4-benzoquinones catalyzed by cuprous(I) chloride was achieved in a solution of acetonitrile and water using molecular dioxygen as an oxidant. Particularly, the inert phenols, such as phenol and mono-alkyl substituted phenols, were effectively oxidized to 1,4-benzoquinones via the selective activation of CH bond in para-position into CO bond under mild conditions. The catalyst shows high activity for unsubstituted or alkyl substituted phenols, but no effect on substituted phenols with electron-withdrawing groups. This study offers an aerobic method for the selective oxidation of aromatic phenols to 1,4-benzoquinones.

Synthesis and characterization of a novel ruthenium(ii) trisbipyridine complex magnetic nanocomposite for the selective oxidation of phenols.

Anchoring ruthenium(ii) trisbipyridine complex [Ru(Bpy)3]2+ into a magnetic dendritic fibrous silica nanostructure produces an unprecedented strong nanocatalyst, FeNi3/DFNS/[Ru(Bpy)3]2+. Impressive oxidation of phenols to 1,4-benzoquinones catalyzed by FeNi3/DFNS/[Ru(Bpy)3]2+ is obtained in acetonitrile and water solution with molecular dioxygen as oxidant. Exclusively, apparently inert phenols such as phenol itself and mono-alkyl-substituted phenols are impressively oxidized to produce 1,4-benzoquinones through activation of the C–H bond in the position para to the carbon–oxygen bond under mild conditions. In addition, the production of industrially significant quinones that are known intermediates for vitamin combinations is investigated and studied FeNi3/DFNS/[Ru(Bpy)3]2+ magnetic nanoparticles were produced, and their properties were investigated by AFM, FTIR, XRD, TGA, SEM, TEM, and VSM.

Photogeneration of Manganese(III) from Luminescent Manganese(II) Complexes with Thiacalixarene Ligands: Synthesis, Structures and Photophysical Properties

The photophysical properties of the compound [(ThiaSO2)(MnII)2(DMF)4(H2O)2] (2), ThiaSO2 = p‐tert‐butylsulfonylcalix[4]arene, are presented and compared to the ones of [(ThiaSO2)2(MnII)4F]K (1). The orange luminescence of 2 is attributed, as for 1, to the MnII centred 4T1→6A1 transition and shows, for this type of complex, the weak influence of the Mn2+ coordination and ThiaSO2 conformation on this luminescence, the temperature and pressure dependence and quenching by molecular dioxygen of which are reported for 2. The latter is attributed to energy transfer from the 4T1 state exciting dioxygen to its 1Σ+g state and is responsible for the photosynthesis of the [(ThiaSO2)(MnIII)(DMF)2]Na (3) complex in DMF solution from 1 or 2. This reaction was studied by UV/Visible and EPR spectroscopy. The molecular structure and EPR spectroscopy of 3 are also presented.

Atomic-Scale Explanation of O2 Activation at the Au-TiO2 Interface.

By a combination of electron paramagnetic resonance spectroscopy, finite-temperature ab initio simulations, and electronic structure analyses, the activation of molecular dioxygen at the interface of gold nanoparticles and titania in Au/TiO2 catalysts is explained at the atomic scale by tracing processes down to the molecular orbital picture. Direct evidence is provided that excess electrons in TiO2, for example created by photoexcitation of the semiconductor, migrate to the gold particles and from there to oxygen molecules adsorbed at gold/titania perimeter sites. Superoxide species are formed more efficiently in this way than on the bare TiO2 surface. This catalytic effect of the gold nanoparticles is attributed to a weakening of the internal O-O bond, leading to a preferential splitting of the molecule at shorter bond lengths together with a 70% decrease of the dissociation free energy barrier compared to the non-catalyzed case on bare TiO2. The findings are an important step forward in the clarification of the role of gold in (photo)catalytic processes.

Aerobic Baeyer-Villiger Oxidation Catalyzed by a Flavin-Containing Enzyme Mimic in Water.

Direct incorporation of molecular oxygen into small organic molecules has attracted much attention for the development of new environmentally friendly oxidation processes. In line with this approach, bioinspired systems mimicking enzyme activities are of particular interest since they may perform catalysis in aqueous media. Demonstrated herein is the incorporation of a natural flavin cofactor (FMN) into the specific microenvironment of a water-soluble polymer which allows the efficient reduction of the FMN by NADH in aqueous solution. Once reduced, this artificial flavoenzyme can then activate molecular dioxygen under aerobic conditions and result in the Baeyer-Villiger reaction at room temperature in water.

(Keynote) The Progress and Challenges in Oxygen Reduction Electrocatalysis without Precious Metals

The focus of this presentation will be the relatively new class of non-precious metal (or platinum group metal-free, PGM-free) electrocatalysts for oxygen reduction reaction (ORR). This particular class of materials has been the subject of a growing interest worldwide since the late 1990s, as one of two main approaches to address the catalyst-cost challenge of polymer electrolyte fuel cells (PEFCs) and some other electrochemical systems that heavily depend on precious metals, typically platinum and its alloys, for oxygen reduction. (With the other approach relying on various ways of Pt thrifting, for example, alloying, core-shell nanoparticle catalyst development, and thin-layer catalyst designs.) The most successful methods of synthesizing PGM-free ORR catalysts typically involve the heat treatment of precursors of transition metals, nitrogen and carbon. These methods have become more sophisticated over the years, yielding catalysts with oxygen reduction activity approaching that of precious metal-based formulations already implemented in the first commercially available fuel cell cars. The most impressive progress in the field appears to have been achieved predominantly via the improvements to the ORR active-site density and catalyst-layer porosity, especially microporosity, using pore-forming agents, sacrificial templates and by other approaches. All the recent progress in PGM-free electrocatalysis notwithstanding, the growing conviction in the electrocatalysis community in the last few years has been that further development of such catalysts hinges on the understanding of the source of the ORR activity in materials without any precious metals and, possibly, without obvious two adjacent active sites for promoting the dissociative mechanism of oxygen reduction. Such understanding is also needed to reveal the reasons for the relatively fast performance loss in fuel cells and also in the electrochemical cells, as well as for the development of remediation strategies, which, together with the activity enhancements, are required to overcome the performance gap between non-precious materials and the incumbent Pt-based cathode catalysts. In this presentation, we will concentrate on both the unquestionable progress in the PGM-free electrocatalysis, accomplished over a relatively short period of time, and significant challenges still facing the field. In the context of challenges, we will summarize efforts specifically targeting better understanding of the sources of PGM-free catalysts activity, identification and quantification of the ORR active sites, and the reaction mechanism, as important steps towards a rational design of catalysts in the future. The results from both theoretical and experimental studies will be presented. Of a number of both in situ and ex situ techniques used for gaining a better insight into the origins of ORR activity in PGM-free catalysts, we will concentrate on the microscopic and X-ray absorption spectroscopic methods, as well as on the implementation of molecular dioxygen analogues as probes for the ORR active sites on the PGM-free catalyst surface, which promises to make otherwise bulk techniques, surface-specific. The characterization part of the presentation will include research performed in close collaboration with partners in the DOE Electrocatalysis Consortium (ElectroCat).

Ascorbate Oxidation by Cu(Amyloid-β) Complexes: Determination of the Intrinsic Rate as a Function of Alterations in the Peptide Sequence Revealing Key Residues for Reactive Oxygen Species Production.

Along with aggregation of the amyloid-β (Aβ) peptide and subsequent deposit of amyloid plaques, oxidative stress is an important feature in Alzheimer's disease. Cu bound to Aβ is able to produce reactive oxygen species (ROS) by the successive reductions of molecular dioxygen, and the ROS produced contribute to oxidative stress. In vitro, ascorbate consumption parallels ROS production, where ascorbate is the reductant that fuels the reactions. Because the affinity of Cu for Aβ is moderate compared to other biomolecules, the rate of ascorbate consumption is a combination of two contributions. The first one is due to peptide-unbound Cu and the second one to peptide-bound Cu complexes. In the present Article, we aim to determine the amounts of the second contribution in the global ascorbate consumption process. It is defined as the intrinsic rate of ascorbate oxidation, which mathematically corresponds to the rate at an infinite peptide to Cu ratio, i.e., without any contribution from peptide-unbound Cu. We show that, for the wild-type Cu(Aβ) complex, this value equals 10% of the value obtained for peptide-unbound Cu and that this value is strongly dependent on peptide alterations. By examination of the dependence of the intrinsic rate of ascorbate oxidation, followed by UV-vis spectroscopy, for several altered peptides, we determine some of the key residues that influence ROS production.

Nonadiabatic one-electron transfer mechanism for the O–O bond formation in the oxygen-evolving complex of photosystem II

The reaction mechanism of the O2 formation in the S4 state of the oxygen-evolving complex of photosystem II was clarified at the quantum mechanics/molecular mechanics (QM/MM) level. After the Yz (Y161) oxidation and the following proton transfer in the S3 state, five reaction steps are required to produce the molecular dioxygen. The highest barrier step is the first proton transfer reaction (0 → 1). The following reactions involving electron transfers were precisely analyzed in terms of their energies, structures and spin densities. We found that the one-electron transfer from the Mn4Ca cluster to Y161 triggers the O–O sigma bond formation.

Kinetico-mechanistic Study on the Oxidation of Biologically Active Iron(II) Bis(thiosemicarbazone) Complexes by Air. Importance of NH···O2 Interactions As Established by Activation Volumes.

Air oxidation of methanolic solutions of biologically active tridentate pyridyl thiosemicarbazone (TSC) complexes of the general formula [FeII(TSC)2] has been studied at varying dioxygen concentrations, temperatures, and pressures. The data collected indicate that the activation entropy of the reaction increases linearly with the redox potential of the complexes in a more definite way than the activation enthalpy. However, a very distinct behavior is observed for the values of the activation volumes, which do not follow the expected entropy-volume parallel trend for all of the systems studied. The involvement of important interactions between the terminal NH groups of the coordinated TSC ligand and molecular dioxygen has been found to be significant by measurements carried out at varying hydrostatic pressures. Kinetic experiments run on analogous N-deuterated complexes confirm the importance of these noncovalent interactions, which are weaker for the less acidic ND groups. These interactions show the existence of an ordering/expansion process upon going from the reactants to the transition state, whenever an interaction between the polar terminal amino groups and dioxygen can be established.

Activation of Molecular Oxygen by a Molybdenum(IV) Imido Compound.

Activation of molecular dioxygen at a molybdenum(IV) imido compound led to the isolation and full characterization of a remarkably stable transition-metal imidoperoxido complex.

Towards a Versatile Photoreactive Platform for Biosensing Applications

An original interfacial hybrid cross-linker molecule combined electrochemical and photochemical properties by substitution of two functional groups, pyrene, and diazirine. The first group enables anchoring by strong π-stacking interaction or by electropolymerization onto multi-walled carbon nanotubes (MWCNT). The other photoreactive group allows the covalent link with biomolecules under long-wavelength UV illumination. Diazirine was chosen due to its ability to photogenerate high reactive radicals under UV irradiation. The photoreactivity of these immobilized nanostructured conductive surfaces was tested towards the covalent attachment of tyrosinase which is well known to oxidize a large range of phenolic compounds and its yield and availability was evaluated by amperometric measurements of catechol by using molecular dioxygen. The architecture exhibiting the best analytical characteristics obtained for catechol was then chosen to detect dopamine.

Structural studies of Neurospora crassa LPMO9D and redox partner CDHIIA using neutron crystallography and small-angle scattering

Sensitivity to hydrogen/deuterium and lack of observable radiation damage makes cold neutrons an ideal probe the structural studies of proteins with highly photosensitive groups such as the copper center of lytic polysaccharide monooxygenases (LPMOs) and flavin adenine dinucleotide (FAD) and heme redox cofactors of cellobiose dehydrogenases (CDHs). Here, neutron crystallography and small-angle neutron scattering are used to investigate Neurospora crassa LPMO9D (NcLPMO9D) and CDHIIA (NcCDHIIA), respectively. The presence of LPMO greatly enhances the efficiency of commercial glycoside hydrolase cocktails in the depolymerization of cellulose. LPMOs can receive electrons from CDHs to activate molecular dioxygen for the oxidation of cellulose resulting in chain cleavage and disruption of local crystallinity. Using neutron protein crystallography, the hydrogen/deuterium atoms of NcLPMO9D could be located throughout the structure. At the copper active site, the protonation states of the side chains of His1, His84, His157 and Tyr168, and the orientation of water molecules could be determined. Small-angle neutron scattering measurements provided low resolution models of NcCDHIIA with both the dehydrogenase and cytochrome domains in oxidized states that exhibited elongated conformations. This work demonstrates the suitability of neutron diffraction and scattering for characterizing enzymes critical to oxidative cellulose deconstruction.