Highly efficient electrocatalytic CO2 reduction by a CrIII quaterpyridine complex.

Design tactics and mechanistic studies both remain as fundamental challenges during the exploitations of earth-abundant molecular electrocatalysts for CO2 reduction, especially for the rarely studied Cr-based ones. Herein, a quaterpyridyl CrIII catalyst is found to be highly active for CO2 electroreduction to CO with 99.8% Faradaic efficiency in DMF/phenol medium. A nearly one order of magnitude higher turnover frequency (86.6 s-1) over the documented Cr-based catalysts (<10 s-1) can be achieved at an applied overpotential of only 190 mV which is generally 300 mV lower than these precedents. Such a high performance at this low driving force originates from the metal-ligand cooperativity that stabilizes the low-valent intermediates and serves as an efficient electron reservoir. Moreover, a synergy of electrochemistry, spectroelectrochemistry, electron paramagnetic resonance, and quantum chemical calculations allows to characterize the key CrII, CrI, Cr0, and CO-bound Cr0 intermediates as well as to verify the catalytic mechanism.

Metamorphic oxygen-evolving molecular Ru and Ir catalysts.

Today sustainable and clean energy conversion strategies are based on sunlight and the use of water as a source of protons and electrons, in a similar manner as it happens in Photosystem II. To achieve this, the charge separation state induced by light has to be capable of oxidising water by 4 protons and 4 electrons and generating molecular oxygen. This oxidation occurs by the intermediacy of a catalyst capable of finding low-energy pathways via proton-coupled electron transfer steps. The high energy involved in the thermodynamics of water oxidation reaction, coupled with its mechanistic complexity, is responsible for the difficulty of discovering efficient and oxidatively robust molecules capable of achieving such a challenging task. A significant number of Ru coordination complexes have been identified as water oxidation catalysts (WOCs) and are among the best understood from a mechanistic perspective. In this review, we describe the catalytic performance of these complexes and focus our attention on the factors that influence their performance during catalysis, especially in cases where a detailed mechanistic investigation has been carried out. The collective information extracted from all the catalysts studied allows one to identify the key features that govern the complex chemistry associated with the catalytic water oxidation reaction. This includes the stability of trans-O-Ru-O groups, the change in coordination number from CN6 to CN7 at Ru high oxidation states, the ligand flexibility, the capacity to undergo intramolecular proton transfer, the bond strain, the axial ligand substitution, and supramolecular effects. Overall, combining all this information generates a coherent view of this complex chemistry.

Supramolecular Anchoring of Fe(III) Molecular Redox Catalysts into Graphitic Surfaces Via CH-π and π-π Interactions for CO2 Electroreduction.

Photoelectrochemical devices require solid anodes and cathodes for the easy assembling of the whole cell and thus redox catalysts need to be deposited on the electrodes. Typical catalyst deposition involves drop casting, spin coating, doctor blading or related techniques to generate modified electrodes where the active catalyst in contact with the electrolyte is only a very small fraction of the deposited mass. We have developed a methodology where the redox catalyst is deposited at the electrode based on supramolecular interactions, namely CH-π and π-π between the catalyst and the surface. This generates a very well-defined catalysts-surface structure and electroactivity, together with a very large catalytic response. This approach represents a new anchoring strategy that can be applied to catalytic redox reactions in heterogeneous phase and compared to traditional methods involves about 4-5 orders of magnitude less mass deposition to achieve comparable activity and with very well-behaved electroactivity and stability.

Interplay between ß-Diimino and ß-Diketiminato Ligands in Nickel Complexes Active in the Proton Reduction Reaction.

Two Ni complexes are reported with κ4-P2N2 ß-diimino (BDI) ligands with the general formula [Ni(XBDI)](BF4)2, where BDI is N-(2-(diphenylphosphaneyl)ethyl)-4-((2-(diphenylphosphaneyl)ethyl)imino)pent-2-en-2-amine and X indicates the substituent in the α-carbon intradiimine position, X = H for 1(BF4)2 and X = Ph for 2(BF4)2. Electrochemical analysis together with UV-vis and NMR spectroscopy in acetonitrile and dimethylformamide (DMF) indicates the conversion of the ß-diimino complexes 12+ and 22+ to the negatively charged ß-diketiminato (BDK) analogues (1-H)+ and (2-H)+ via deprotonation in DMF. Moreover, further electrochemical and spectroscopy evidence indicates that the one-electron-reduced derivatives 1+ and 2+ can also rapidly evolve to the BDK (1-H)+ and (2-H)+, respectively, via hydrogen gas evolution through a bimolecular homolytic pathway. Finally, both complexes are demonstrated to be active for the proton reduction reaction in DMF at Eapp = -1.8 V vs Fc+/0, being the active species the one-electron-reduced derivative 1-H and 2-H.

Unravelling the Mechanistic Pathway of the Hydrogen Evolution Reaction Driven by a Cobalt Catalyst.

A cobalt complex bearing a κ-N3 P2 ligand is presented (1+ or CoI (L), where L is (1E,1'E)-1,1'-(pyridine-2,6-diyl)bis(N-(3-(diphenylphosphanyl)propyl)ethan-1-imine). Complex 1+ is stable under air at oxidation state CoI thanks to the π-acceptor character of the phosphine groups. Electrochemical behavior of 1+ reveals a two-electron CoI /CoIII oxidation process and an additional one-electron reduction, which leads to an enhancement in the current due to hydrogen evolution reaction (HER) at Eonset =-1.6 V vs Fc/Fc+ . In the presence of 1 equiv of bis(trifluoromethane)sulfonimide, 1+ forms the cobalt hydride derivative CoIII (L)-H (22+ ), which has been fully characterized. Further addition of 1 equiv of CoCp*2 (Cp* is pentamethylcyclopentadienyl) affords the reduced CoII (L)-H (2+ ) species, which rapidly forms hydrogen and regenerates the initial CoI (L) (1+ ). The spectroscopic characterization of catalytic intermediates together with DFT calculations support an unusual bimolecular homolytic mechanism in the catalytic HER with 1+ .

Surface-Promoted Evolution of Ru-bda Coordination Oligomers Boosts the Efficiency of Water Oxidation Molecular Anodes.

A new Ru oligomer of formula {[RuII(bda-κ-N2O2)(4,4'-bpy)]10(4,4'-bpy)}, 10 (bda is [2,2'-bipyridine]-6,6'-dicarboxylate and 4,4'-bpy is 4,4'-bipyridine), was synthesized and thoroughly characterized with spectroscopic, X-ray, and electrochemical techniques. This oligomer exhibits strong affinity for graphitic materials through CH-π interactions and thus easily anchors on multiwalled carbon nanotubes (CNT), generating the molecular hybrid material 10@CNT. The latter acts as a water oxidation catalyst and converts to a new species, 10'(H2O)2@CNT, during the electrochemical oxygen evolution process involving solvation and ligand reorganization facilitated by the interactions of molecular Ru catalyst and the surface. This heterogeneous system has been shown to be a powerful and robust molecular hybrid anode for electrocatalytic water oxidation into molecular oxygen, achieving current densities in the range of 200 mA/cm2 at pH 7 under an applied potential of 1.45 V vs NHE. The remarkable long-term stability of this hybrid material during turnover is rationalized based on the supramolecular interaction of the catalyst with the graphitic surface.

Synthesis, Structure, and Ammonia Oxidation Catalytic Activity of Ru-NH3 Complexes Containing Multidentate Polypyridyl Ligands.

Ammonia (electro)oxidation with molecular catalysts is a rapidly developing topic with wide practical applications ahead. We report here the catalytic ammonia oxidation reaction (AOR) activity using [Ru(tda-κ-N3O)(py)2], 2, (tda2- is 2,2':6',2''-terpyridine-6,6''-dicarboxylate; py is pyridine) as a catalyst precursor. Furthermore, we also describe the rich chemistry associated with the reaction of Ru-tda and Ru-tPa (tPa-4 is 2,2':6',2''-terpyridine-6,6''-diphosphonate) complexes with NH3 and N2H4 using [RuII(tda-κ-N3O)(dmso)Cl] (dmso is dimethyl sulfoxide) and [RuII(tPa-κ-N3O)(py)2], 8, as synthetic intermediates, respectively. All the new complexes obtained here were characterized spectroscopically by means of UV-vis and NMR. In addition, a crystal X-ray diffraction analysis was performed for complexes trans-[RuII(tda-κ-N3)(py)2(NH3)], 4, trans-[RuII(tda-κ-N3)(N-NH2)(py)2], 5, cis-[RuII(tda-κ-N3)(py)(NH3)2], 6 (30%), and cis-[RuII(tda-k-N3)(dmso)(NH3)2], 7 (70%). The AOR activity associated with 2 and 8 as catalyst precursors was studied in organic and aqueous media. For 2, turnover numbers of 7.5 were achieved under bulk electrolysis conditions at an Eapp = 1.4 V versus normal hydrogen electrode in acetonitrile. A catalytic cycle is proposed based on electrochemical and kinetic evidence.

Consecutive Ligand-Based Electron Transfer in New Molecular Copper-Based Water Oxidation Catalysts.

Water oxidation to dioxygen is one of the key reactions that need to be mastered for the design of practical devices based on water splitting with sunlight. In this context, water oxidation catalysts based on first-row transition metal complexes are highly desirable due to their low cost and their synthetic versatility and tunability through rational ligand design. A new family of dianionic bpy-amidate ligands of general formula H2 LNn- (LN is [2,2'-bipyridine]-6,6'-dicarboxamide) substituted with phenyl or naphthyl redox non-innocent moieties is described. A detailed electrochemical analysis of [(L4)Cu]2- (L4=4,4'-(([2,2'-bipyridine]-6,6'-dicarbonyl)bis(azanediyl))dibenzenesulfonate) at pH 11.6 shows the presence of a large electrocatalytic wave for water oxidation catalysis at an η=830 mV. Combined experimental and computational evidence, support an all ligand-based process with redox events taking place at the aryl-amide groups and at the hydroxido ligands.

Redox Metal-Ligand Cooperativity Enables Robust and Efficient Water Oxidation Catalysis at Neutral pH with Macrocyclic Copper Complexes.

Water oxidation catalysis stands out as one of the most important reactions to design practical devices for artificial photosynthesis. Use of late first-row transition metal (TM) complexes provides an excellent platform for the development of inexpensive catalysts with exquisite control on their electronic and structural features via ligand design. However, the difficult access to their high oxidation states and the general labile character of their metal-ligand bonds pose important challenges. Herein, we explore a copper complex (12-) featuring an extended, π-delocalized, tetra-amidate macrocyclic ligand (TAML) as water oxidation catalyst and compare its activity to analogous systems with lower π-delocalization (22- and 32-). Their characterization evidences a special metal-ligand cooperativity in accommodating the required oxidative equivalents using 12- that is absent in 22- and 32-. This consists of charge delocalization promoted by easy access to different electronic states at a narrow energy range, corresponding to either metal-centered or ligand-centered oxidations, which we identify as an essential factor to stabilize the accumulated oxidative charges. This translates into a significant improvement in the catalytic performance of 12- compared to 22- and 32- and leads to one of the most active and robust molecular complexes for water oxidation at neutral pH with a kobs of 140 s-1 at an overpotential of only 200 mV. In contrast, 22- degrades under oxidative conditions, which we associate to the impossibility of efficiently stabilizing several oxidative equivalents via charge delocalization, resulting in a highly reactive oxidized ligand. Finally, the acyclic structure of 32- prevents its use at neutral pH due to acidic demetalation, highlighting the importance of the macrocyclic stabilization.

Synthesis, Electrochemical Characterization, and Water Oxidation Chemistry of Ru Complexes Containing the 2,6-Pyridinedicarboxylato Ligand.

The tridentate meridional ligand pyridyl-2,6-dicarboxylato (pdc2-) has been used to prepare complexes [RuII(pdc-κ3-N1O2)(DMSO)2Cl]- (1II), [RuII(pdc-κ3-N1O2)(bpy)(DMSO)] (2II), and {[RuIII(pdc-κ3-N1O2)(bpy)]2(µ-O)} (5III,III), where bpy = 2,2'-bipyridine. All complexes have been fully characterized through spectroscopic, electrochemical, and single-crystal X-ray diffraction techniques. Compounds 1II and 2II show S → O linkage isomerization of the DMSO ligand upon oxidation from RuII to RuIII, and thermodynamic and kinetic data have been obtained from cyclic voltammetry experiments. Dimeric complex 5III,III is a precursor of the monomeric complex [RuII(pdc-κ3-N1O2)(bpy)(H2O)] (4II) which is a water oxidation catalyst. The electrochemistry and catalytic activity of 4II has been ascertained for the first time and compared with related Ru-aquo complexes that are also active for the water oxidation reaction. It shows a TOFmax = 0.2 s-1 and overpotential of 240 mV in pH = 1. The overpotential shown by 4II is one of the lowest reported in the literature and is associated with the role of the two carboxylato groups of the pdc ligand, providing high electron density to the ruthenium complex.

Effect of Ligand Chelation and Sacrificial Oxidant on the Integrity of Triazole-Based Carbene Iridium Water Oxidation Catalysts.

We report the effect of replacing the pyridine group in the chelating trz Ir-water oxidation catalysts by a benzoxazole and a thiazole moiety. We have also evaluated if the presence of bidentate ligands is crucial for high activities and to avoid the decomposition into undesired heterogeneous layers. The catalytic performance of these benzoxazole/thiazole-triazolidene Ir-complexes in water oxidation was studied at variable pH using either CAN (pH = 1) or NaIO4 (pH = 5.6 and 7). Electrocatalytic experiments indicated that while CAN-mediated water oxidation led to catalyst heterogeneization irrespective of the triazolylidene substituent, periodate as sacrificial oxidant preserved a homogeneously active species. Repetitive additions of sacrificial oxidant indicates higher integrity of the Ir-complex with a thiazole-substituted triazolylidene compared to ligands featuring a benzoxazole as chelating donor or no chelating group at all. Rigid chelation of the thiazole group was also established from stability measurements under highly acidic, oxidizing, and high ionic strength conditions.

Electrocatalytic CO2 Reduction by Imidazolium-Functionalized Molecular Catalysts.

We present the first examples of CO2 electro-reduction catalysts that feature charged imidazolium groups in the secondary coordination sphere. The functionalized Lehn-type catalysts display significant differences in their redox properties and improved catalytic activities as compared to the conventional reference catalyst. Our results suggest that the incorporated imidazolium moieties do not solely function as a charged tag but also alter mechanistic aspects of catalysis.

Synthesis and Isomeric Analysis of RuII Complexes Bearing Pentadentate Scaffolds.

A RuII-pentadentate polypyridyl complex [RuII(κ-N5-bpy2PYMe)Cl]+ (1+, bpy2PYMe = 1-(2-pyridyl)-1,1-bis(6-2,2'-bipyridyl)ethane) and its aqua derivative [RuII(κ-N5-bpy2PYMe)(H2O)]2+ (22+) were synthesized and characterized by experimental and computational methods. In MeOH, 1+ exists as two isomers in different proportions, cis (70%) and trans (30%), which are interconverted under thermal and photochemical conditions by a sequence of processes: chlorido decoordination, decoordination/recoordination of a pyridyl group, and chlorido recoordination. Under oxidative conditions in dichloromethane, trans-12+ generates a [RuIII(κ-N4-bpy2PYMe)Cl2]+ intermediate after the exchange of a pyridyl ligand by a Cl- counterion, which explains the trans/cis isomerization observed when the system is taken back to Ru(II). On the contrary, cis-12+ is in direct equilibrium with trans-12+, with absence of the κ-N4-bis-chlorido RuIII-intermediate. All these equilibria were modeled by density functional theory calculations. Interestingly, the aqua derivative is obtained as a pure trans-[RuII(κ-N5-bpy2PYMe)(H2O)]2+ isomer (trans-22+), while the addition of a methyl substituent to a single bpy of the pentadentate ligand leads to the formation of a single cis isomer for both chlorido and aqua derivatives [RuII(κ-N5-bpy(bpyMe)PYMe)Cl]+ (3+) and [RuII(κ-N5-bpy(bpyMe)PYMe)(H2O)]2+ (42+) due to the steric constraints imposed by the modified ligand. This system was also structurally and electrochemically compared to the previously reported [RuII(PY5Me2)X]n+ system (X = Cl, n = 1 (5+); X = H2O, n = 2 (62+)), which also contains a κ-N5-RuII coordination environment, and to the newly synthesized [RuII(PY4Im)X]n+ complexes (X = Cl, n = 1 (7+); X = H2O, n = 2 (82+)), which possess an electron-rich κ-N4C-RuII site due to the replacement of a pyridyl group by an imidazolic carbene.

Powerful Bis-facially Pyrazolate-Bridged Dinuclear Ruthenium Epoxidation Catalyst.

A new bis-facial dinuclear ruthenium complex, {[Ru(II)(bpy)]2(µ-bimp)(µ-Cl)}(2+), 2(2+), containing a hexadentate pyrazolate-bridging ligand (Hbimp) and bpy as auxiliary ligands has been synthesized and fully characterized in solution by spectrometric, spectroscopic, and electrochemical techniques. The new compound has been tested with regard to its capacity to oxidize water and alkenes. The in situ generated bis-aqua complex, {[Ru(II)(bpy)(H2O)]2(µ-bimp)}(3+), 3(3+), is an excellent catalyst for the epoxidation of a wide range of alkenes. High turnover numbers (TN), up to 1900, and turnover frequencies (TOF), up to 73 min(-1), are achieved using PhIO as oxidant. Moreover, 3(3+) presents an outstanding stereospecificity for both cis and trans olefins toward the formation of their corresponding epoxides due to specific interactions transmitted by its ligand scaffold. A mechanistic analysis of the epoxidation process has been performed based on density functional theory (DFT) calculations in order to better understand the putative cooperative effects within this dinuclear catalyst.

Robust Molecular Anodes for Electrocatalytic Water Oxidation Based on Electropolymerized Molecular Cu Complexes.

A multistep synthesis of a new tetra-amidate macrocyclic ligand functionalized with alkyl-thiophene moieties, 15,15-bis(6-(thiophen-3-yl)hexyl)-8,13-dihydro-5H-dibenzo[b,h][1,4,7,10]tetraazacyclotridecine-6,7,14,16(15H,17H)-tetraone, H4 L, is reported. The reaction of the deprotonated ligand, L4- , and Cu(II) generates the complex [LCu]2- , that can be further oxidized to Cu(III) with iodine to generate [LCu]- . The H4 L ligand and their Cu complexes have been thoroughly characterized by analytic and spectroscopic techniques (including X-ray Absorption Spectroscopy, XAS). Under oxidative conditions, the thiophene group of [LCu]2- complex polymerizes on the surface of graphitic electrodes (glassy carbon disks (GC), glassy carbon plates (GCp ), carbon nanotubes (CNT), or graphite felts (GF)) generating highly stable thin films. With CNTs deposited on a GC by drop casting, hybrid molecular materials labeled as GC/CNT@p-[LCu]2- are obtained. The latter are characterized by electrochemical techniques that show their capacity to electrocatalytically oxidize water to dioxygen at neutral pH. These new molecular anodes achieve current densities in the range of 0.4 mA cm-2 at 1.30 V versus NHE with an onset overpotential at ≈250 mV. Bulk electrolysis experiments show an excellent stability achieving TONs in the range of 7600 during 24 h with no apparent loss of catalytic activity and maintaining the molecular catalyst integrity, as evidenced by electrochemical techniques and XAS spectroscopy.

Heterogeneous Electrochemical Ammonia Oxidation with a Ru-bda Oligomer Anchored on Graphitic Electrodes via CH-π Interactions.

Molecular catalysts can promote ammonia oxidation, providing mechanistic insights into the electrochemical N2 cycle for a carbon-free fuel economy. We report the ammonia oxidation activity of carbon anodes functionalized with the oligomer {[RuII(bda-κ-N 2 O 2)(4,4'-bpy)]10(4,4'-bpy)}, Rubda-10, where bda is [2,2'-bipyridine]-6,6'-dicarboxylate and 4,4'-bpy is 4,4'-bipyridine. Electrocatalytic studies in propylene carbonate demonstrate that the Ru-based hybrid anode used in a 3-electrode configuration transforms NH3 to N2 and H2 in a 1:3 ratio with near-unity faradaic efficiency at an applied potential of 0.1 V vs Fc+/0, reaching turnover numbers of 7500. X-ray absorption spectroscopic analysis after bulk electrolysis confirms the molecular integrity of the catalyst. Based on computational studies together with electrochemical evidence, ammonia nucleophilic attack is proposed as the primary pathway that leads to critical N-N bond formation.

Mapping the Ultrafast Mechanistic Pathways of Co Photocatalysts in Pure Water through Time-Resolved X-ray Spectroscopy.

Nanosecond time-resolved X-ray (tr-XAS) and optical transient absorption spectroscopy (OTA) are applied to study 3 multimolecular photocatalytic systems with [Ru(bpy)3 ]2+ photoabsorber, ascorbic acid electron donor and Co catalysts with methylene (1), hydroxomethylene (2) and methyl (3) amine substituents in pure water. OTA and tr-XAS of 1 and 2 show that the favored catalytic pathway involves reductive quenching of the excited photosensitizer and electron transfer to the catalyst to form a CoII square pyramidal intermediate with a bonded aqua molecule followed by a CoI square planar derivative that decays within ≈8 µs. By contrast, a CoI square pyramidal intermediate with a longer decay lifetime of ≈35 µs is formed from an analogous CoII geometry for 3 in H2 O. These results highlight the protonation of CoI to form the elusive hydride species to be the rate limiting step and show that the catalytic rate can be enhanced through hydrogen containing pendant amines that act as H-H bond formation proton relays.

Electrocatalytic water oxidation from a mixed linker MOF based on NU-1000 with an integrated ruthenium-based metallo-linker.

A novel tetratopic metallo-linker, [Ru(tda)(py(PhCOOH)2)2], 1, (tda = 2,2':6',2''-terpyridine-6,6''-dicarboxylate; py(PhCOOH)2 = (4,4'-(pyridine-3,5-diyl)dibenzoic acid), that is structurally based on one of the most active molecular water oxidation catalysts has been prepared and fully characterized, including single crystal X-ray diffraction. 1 bears geometric similarities to H4TBAPy (H4TBAPy = 4,4',4'',4'''-(pyrene-1,3,6,8-tetrayl)tetrabenzoic acid), i.e. the native linker in NU-1000, which offers the possibility to synthesize NU-1000-Ru mixed linker MOFs solvothermally. Mixed linker MOF formation was demonstrated by powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM), and Ru linker incorporation confirmed by FT-IR, energy-dispersive X-ray (EDX) spectroscopy and inductively coupled plasma optical emission spectroscopy (ICP-OES). It was found that the Ru contents in the final mixed linker MOFs correlate with the amount of Ru linker present during solvothermal synthesis, albeit not in a linear fashion. The cyclic voltammograms (CV) of the mixed linker MOFs are largely dominated by TBAPy-based oxidations with features attributed to 1. Interestingly, Ru linkers near the crystal surface are oxidized directly by interfacial hole transfer form the electrode, while those in the crystal interior can be oxidized indirectly from oxidized TBAPy linkers at more anodic potential. Upon repeated scanning, the CVs show the appearance of new waves that arise from irreversible TBAPy oxidation, as well as from the activation of the Ru-based water oxidation catalyst. Of the materials prepared, the one with the highest Ru content, NU-1000-Ruhigh, was shown to catalyze the electrochemical oxidation of water to dioxygen. The Faradaic efficiency (FE) of the construct is 37%, due to water oxidation being accompanied by oxidative transformations of the TBAPy linkers. Despite the low FE, NU-1000-Ruhigh is still among the best MOF-based water oxidation catalysts, operating by a unique co-linker mediated hole-transport mechanism to supply oxidizing equivalents also to catalysts in the crystal interior.

Chemical strategies for triggering the immune response to the mycotoxin patulin.

Mycotoxins represent a major concern for human and animal health because of their harmful effects and high occurrence in food and feed. Rapid immunoanalytical methods greatly contribute to strengthening the safety of our food supply by efficiently monitoring chemical contaminants, so high-affinity and specific antibodies have been generated for almost all internationally regulated mycotoxins. The only exception is patulin, a mycotoxin mainly produced by Penicillium expansum for which such a target has not yet been achieved. Accordingly, no point-of-need tests commonly used in food immunodiagnostics are commercially available for patulin. In the present study, three functionalized derivatives conforming to generally accepted rules in hapten design were firstly tested to generate suitable antibodies for the sensitive immunodetection of patulin. However, these conventional bioconjugates were unable to elicit the desired immune response, so an alternative strategy that takes advantage of the high electrophilic reactivity of patulin was explored. Patulin was reacted with 4-bromothiophenol, and the obtained adduct was used to produce antibodies with nanomolar affinity values. These results demonstrated for the first time that targeting the adduct resulting from the reaction of patulin with a thiol-containing compound is a promising approach for developing user-friendly immunoanalytical techniques for this elusive mycotoxin.

A broad view on the complexity involved in water oxidation catalysis based on Ru-bpn complexes.

A new Ru complex with the formula [Ru(bpn)(pic)2]Cl2 (where bpn is 2,2'-bi(1,10-phenanthroline) and pic stands for 4-picoline) (1Cl2) is synthesized to investigate the true nature of active species involved in the electrochemical and chemical water oxidation mediated by a class of N4 tetradentate equatorial ligands. Comprehensive electrochemical (by using cyclic voltammetry, differential pulse voltammetry, and controlled potential electrolysis), structural (X-ray diffraction analysis), spectroscopic (UV-vis, NMR, and resonance Raman), and kinetic studies are performed. 12+ undergoes a substitution reaction when it is chemically (by using NaIO4) or electrochemically oxidized to RuIII, in which picoline is replaced by an hydroxido ligand to produce [Ru(bpn)(pic)(OH)]2+ (22+). The former complex is in equilibrium with an oxo-bridged species {[Ru(bpn)(pic)]2(µ-O)}4+ (34+) which is the major form of the complex in the RuIII oxidation state. The dimer formation is the rate determining step of the overall oxidation process (kdimer = 1.35 M-1 s-1), which is in line with the electrochemical data at pH = 7 (kdimer = 1.4 M-1 s-1). 34+ can be reduced to [Ru(bpn)(pic)(OH2)]2+ (42+), showing a sort of square mechanism. All species generated in situ at pH 7 have been thoroughly characterized by NMR, mass spectrometry, UV-Vis and electrochemical techniques. 12+ and 42+ are also characterized by single crystal X-ray diffraction analysis. Chemical oxidation of 12+ triggered by CeIV shows its capability to oxidize water to dioxygen.