Kinetics and mechanism of osmium(VIII)-catalyzed oxidation of 1,4-thioxane by alkaline hexacyanoferrate(III)

The kinetics of oxidation of 1,4-thioxane (1,4-oxathiane) by alkaline K₃Fe(CN)₆ have been studied in the presence of Os^VIII as catalyst. The reaction is first order in hexacyanoferrate(III) and Os^VIII. The order in thioxane and OH^– is zero. While added salts and ethanol have a negligible effect on the oxidation rate, K₄Fe(CN)₆ retards it. On the basis of kinetic evidence, a mechanism has been proposed.     

Hexacyanoferrate‐based ionic liquids as Fenton‐like catalysts for deep oxidative desulfurization of fuels

Two hexacyanoferrate‐based ionic liquids, [C₄Py]₃Fe(CN)₆ and [C₁₆Py]₃Fe(CN)₆, were synthesized and characterized using Fourier transform infrared and mass spectroscopies and CHN analysis. They were employed as Fenton‐like catalysts in extraction and catalytic oxidative desulfurization of model oil with dibenzothiophene (DBT), benzothiophene (BT), 4,6‐dimethyldibenzothiophene (4,6‐DMDBT), 4‐methyldibenzothiophene (4‐MDBT) and 3‐methylbenzothiophene (3‐MBT) as substrates. Various polar solvents, such as ionic liquids, water and organic solvents, were applied to choose a suitable extractant. The results showed the removal of DBT reached 97.1% with [C₄Py]₃Fe(CN)₆ as a catalyst and 1‐n‐octyl‐3‐methylimidazolium hexafluorophosphate ([C₈mim]PF₆) as an extractant under optimal conditions. The activity of sulfur removal followed the order DBT > 3‐MBT > BT > 4‐MDBT >4,6‐DMDBT. The effect of water content on sulfur removal was investigated by adding various concentrations of H₂O₂. It was found that excess water had a positive effect on sulfur removal but the catalysts were less sensitive than [FeCl₄^?]‐based catalysts to water. The mechanism was studied using electron spin‐resonance spectroscopy and gas chromatography–mass spectrometry. O₂^?? may be the active oxygen species in the catalytic oxidative desulfurization process and the oxidation products of various sulfur compounds were the corresponding sulfoxides and sulfones. Copyright © 2016 John Wiley & Sons, Ltd.     

Fe/Zn double metal cyanide catalyzed ring-opening polymerization of propylene oxide: 2. Characterization of active structure of double metal cyanide catalysts

Double metal cyanide (DMC) complexes based on Zn₃[Fe(CN)₆]₂ were synthesized using different molar ratios of ZnCl₂ to K₃[Fe(CN)₆] and special complexing agents. IR spectroscopy, electron spectroscopy for chemical analysis, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and other analytical techniques were employed to characterize these catalysts. The morphology and structure of these DMC catalysts were attributed to the different complexing agents as well as to the different molar ratios of ZnCl₂ to K₃[Fe(CN)₆]. In addition, the catalytic activity was strongly correlated with the morphology and noncrystalline content of DMC catalysts. High-activity catalysts could be prepared by controlling the structure of DMC catalysts by incorporating complexing agents. The active species of DMC catalysts for ring-opening polymerization are Zn²⁺, [Fe(CN)₆]^3–, Cl^–, and the compound of their ligands.     

Use of Screen‐printed Electrodes Modified by Prussian Blue and Analogues in Sensing of Cysteine

The utilisation of screen‐printing technology allows for a mass scalable approach for the production of electrochemical screen‐printed electrodes (SPEs) and the presence of a redox mediator can add new possibilities to the electrochemical properties of the SPEs. Among the materials used as redox mediators, cyanidoferrates polymers can be used for electro‐oxidation of cysteine. In this work, two monomers, namely, [Fe(CN)₆]⁴⁻ and [Fe(CN)₅NH₃]³⁻ were used to produce Prussian blue (PB) and Prussian blue‐Ammine (PB‐Ammine), respectively. In addition, two modification methods were compared, firstly via a drop‐casting and secondly by the incorporation of these materials into a printable ink. The SPE modified by PB‐Ammine (drop‐casting) exhibits the highest electroactive area, however the highest heterogeneous rate constant was found with the SPE modified by PB‐Ammine that was incorporated into the ink. The highest value of the constant of electro‐oxidation of cysteine and lowest limit of detection was also observed in the SPE modified by PB incorporated into the ink. These studies suggest that the electrocatalytic properties of SPE modified by PB and PB‐Ammine are dependent upon the availability of Fe³⁺ catalytic sites and the increased kinetics of the chemical reaction between the catalytic sites and the analyte.     

Preparation of57Fe enriched K4[Fe(CN)6] and K3[Fe(CN)6]

A simple method to prepare⁵⁷Fe enriched K₄[Fe(CN)₆] and K₃[Fe(CN)₆] is described. The yields of the products are much better than those reported in the literature so far. The enrichment is essential for⁵⁷Fe Mössbauer investigation in a variety of Prussiate type complexes and other inorganic compounds which are conveniently prepared from K₄[Fe(CN)₆] and K₃[Fe(CN)₆]. K₄[Fe(CN)₆] was obtained by reacting freshly prepared Fe(OH)₃ with glacial acetic acid and treating with iron acetate in boiling aqueous solution of KCN. The novel feature of the procedure to obtain K₃[Fe(CN)₆] is that the oxidation of K₄[Fe(CN)₆] has been carried out in the solid state by passing chlorine gas over the powdered specimen. K₃[Fe(CN)₆] was crystallised from alkaline solution of this oxidised powder. The compounds were characterised by Mössbauer spectroscopy.     

Isolated Single Iron Atoms Anchored on N‐Doped Porous Carbon as an Efficient Electrocatalyst for the Oxygen Reduction Reaction

The development of low‐cost, efficient, and stable electrocatalysts for the oxygen reduction reaction (ORR) is desirable but remains a great challenge. Herein, we made a highly reactive and stable isolated single‐atom Fe/N‐doped porous carbon (ISA Fe/CN) catalyst with Fe loading up to 2.16 wt %. The catalyst showed excellent ORR performance with a half‐wave potential (E _1/2) of 0.900 V, which outperformed commercial Pt/C and most non‐precious‐metal catalysts reported to date. Besides exceptionally high kinetic current density (J _k) of 37.83 mV cm⁻² at 0.85 V, it also had a good methanol tolerance and outstanding stability. Experiments demonstrated that maintaining the Fe as isolated atoms and incorporating nitrogen was essential to deliver the high performance. First principle calculations further attributed the high reactivity to the high efficiency of the single Fe atoms in transporting electrons to the adsorbed OH species.     

Osmium(VIII)-catalyzed oxidation of pentamethylene sulfide

Although pentamethylene sulfide (tetrahydrothiopyran) lacks acidic hydrogen, Os^VIII has been found to catalyze its oxidation by alkaline K₃Fe(CN)₆ to produce 3-hydroxypentamethylene sulfide as the only product. The kinetics reveal first-order dependence on ferricyanide and Os^VIII, and zero order on pentamethylene sulfide and OH^–. The effects of introduced electrolytes, K₄Fe(CN)₆, relative permittivity and temperature have also been studied. On the basis of kinetic evidence, a mechanism that involves anation of the osmium catalyst (sulfide/water interchange) followed by intramolecular proton abstraction, followed by an electron transfer step has been proposed and discussed.     

Cyano‐Bridged Aqua(N,N‐Dimethylacetamide)(cyanoiron)lanthanides from Samarium,Gadolinium, or Holmium Nitrate and Potassium Hexacyanoferrate: Crystal Structures and Magnetochemistry

Three cyano‐bridged aqua(N,N‐dimethylacetamide)(cyanoiron)lanthanide complexes were synthesized by the reaction of K₃Fe(CN)₆, Ln(NO₃)₃⋅6 H₂O (Ln=Sm, Gd, Ho), and N,N‐dimethylacetamide (DMA). The obtained complexes 1 – 3 exhibit different coordination geometries and crystal structures. The polymeric {[Sm(DMA)₂(H₂O)₄Fe(CN)₆⋅5 H₂O}_n ([SmFe]_n; 1 ) has a one‐dimensional chain structure with approximately parallel trans‐positioned bridging CN ligands between the Sm‐ and Fe‐atoms. [(Gd(DMA)₃(H₂O)₄)₂Fe(CN)₆]⋅[Fe(CN)₆]⋅3 H₂O (Gd₂Fe; 2 ) is an isolated trinuclear Gd(1)−Fe−Gd(2) complex with two approximately perpendicular cis‐positioned bridging CN ligands between the two Gd‐atoms and the Fe‐atom. [Ho(DMA)₃(H₂O)₃Fe(CN)₆]⋅3 H₂O (HoFe; 3 ) adopts a single dinuclear crystal structure with only one bridging CN between the Ho‐ and Fe‐atom. Magnetochemistry experiments establish weak antiferromagnetic interactions between Gd^III (and Ho^III) and Fe^III atoms. Especially the [SmFe]_n complex 1 exhibits long‐range magnetic ordering, T_c=3.5 K, and a stronger coercive force, H_c=1400 Oe.     

Electrochemical Behavior of K3[Fe(CN)6] on the Electrode Coated with Modified Multi‐Walled Carbon Nanotubes

The electrochemical behavior of K₃[Fe(CN)₆] was studied on an ITO electrode that was coated with β‐cyclodextrin (CD) modified multi‐walled carbon nanotubes (MWNTs) and with carboxyl modified multi‐walled carbon nanotubes (MWNT‐COOHs). MWNT‐COOHs showed an excellent electrocatalytic effect on the redox of K₃[Fe(CN)₆] while MWNT‐CDs had a subdued effect on the electrochemical response of K₃[Fe(CN)₆]. It is probably due to mismatching between K₃[Fe(CN)₆] and cyclodextrin, which hampers the contact of K₃[Fe(CN)₆] with carbon nanotubes. Moreover, the electrochemical behavior of K₃[Fe(CN)₆] on the MWNT‐COOHs coated ITO electrode at various scan rates also was measured. The results indicated that both potential difference between redox peaks and peak current of K₃[Fe(CN)₆] increased with increasing scan rate. A good linearity of peak current versus scan rate was observed.     

Cocatalysis by ruthenium(III) in hydrogen ions catalyzed oxidation of iodide ions: A kinetic study

RuCl₃ further catalyzes the oxidation of iodide ion by K₃Fe(CN)₆, already catalyzed by hydrogen ions. The rate of reaction, when catalyzed only by hydrogen ions, was separated graphically from the rate when both Ru(III) and H⁺ ions catalyzed the reaction. Reactions studied separately in the presence as well as absence of RuCl₃ under similar conditions were found to follow second‐order kinetics with respect to [I^?], while the rate showed direct proportionality with respect to [Fe(CN)₆]^3?, [RuCl₃], and [H⁺]. External addition of [Fe(CN)₆]^4? ions retards the reaction velocity, while changing the ionic strength of the medium has no effect on the rate. With the help of the intercept of the catalyst graph, the extent of the reaction that takes place without adding Ru(III) was calculated and it was in accordance with the values obtained from the reaction in which only H⁺ ions catalyzed the reaction. It is proposed that ruthenium forms a complex, which slowly disproportionates into the rate‐determining step. Arrhenius parameters at four different temperatures were also calculated. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 545–553, 2004     

Mechanisms of oxidation of K4Fe(CN)6 by hypochlorous acid and catalytic activation by azide, bromide, and iodide

Summary HOCl reacts with Fe(CN) ₆ ^4– to generate an intermediate, presumably FeCl(CN) ₆ ^3– , which exhibits a weak absorption around 282 nm and decays simultaneously with the formation of Fe(CN) ₆ ^3– . When decreasing the HOCl/Fe(CN) ₆ ^4– concentration ratio fromR>1 toR<1, a drastic change in the kinetics of the oxidation is observed. Depending onR, the intermediate obviously oxidizes either Fe(CN) ₆ ^4– or HOCl. AtR1, a further intermediate appears which also precedes the oxidation and absorbs strongly around 360 nm. The intermediates detected may represent reactive high oxidation states of iron (Fe(IV) and Fe(VI)). HOCl induced oxidation of Fe(CN) ₆ ^4– is activated catalytically by Br^–, I^–, and N ₃ ^– , obviously due to generation of stronger oxidants (HOBr, HOI, and ClN₃), but oxidation is efficiently inhibited by CN^– and NCS^–.

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Mechanismen der Oxidation von K₄Fe(CN)₆ durch Hypochlorsäure und katalytische Aktivierung durch Azid, Bromid und Iodid

Zusammenfassung HOCl reagiert mit Fe(CN) ₆ ^4– unter Bildung eines Intermediats, vermutlich FeCl(CN) ₆ ^3– , das bei 282 nm eine schwache Absorption aufweist und parallel zum Erscheinen von Fe(CN) ₆ ^3– verschwindet. Man beobachtet eine drastische Änderung in der Oxidationskinetik, wenn das HOCl/Fe(CN) ₆ ^4– Konzentrationsverhältnis vonR>1 zuR<1 verändert wird. In Abhängigkeit vonR wird offenbar entweder Fe(CN) ₆ ^4– oder HOCl durch das Intermediat oxidiert. FürR1 erscheint ein weiteres Intermediat mit einer starken Absorptionsbande bei 360 nm, das ebenfalls der Oxidation vorangeht. Bei den beobachteten Intermediaten handelt es sich vermutlich um reaktive höhere Oxidationsstufen des Eisens (Fe(IV) und Fe(VI)). Die HOCl-induzierte Oxidation von Fe(CN) ₆ ^4– wird einerseits durch Br^–, I^– und N ₃ ^– katalytish aktiviert (offenbar infolge der Bildung stärkerer Oxidantien wie HOBr, HOI und ClN₃), andererseits durch CN^– und NCS^– effektiv inhibiert.

     

Ferricyanide Armed Anodes Enable Stable Water Oxidation in Saturated Saline Water at 2 A/cm2

The direct seawater electrolysis at high current density and low overpotential affords an effective strategy toward clean and renewable hydrogen fuel production. However, the severe corrosion of anode as a result of the saturation of Cl⁻ upon continuous seawater feeding seriously hamper the electrolytic process. Herein, cobalt ferricyanide / cobalt phosphide (CoFePBA/Co₂P) anodes with Cap/Pin structure are synthesized, which stably catalyze alkaline saturated saline water oxidation at 200–2000 mA cm⁻² over hundreds of hours without corrosion. Together with the experimental findings, the molecular dynamics simulations reveal that PO₄³⁻ and Fe(CN)₆³⁻ generated by the electrode play synergistic role in repelling Cl⁻ via electrostatic repulsion and dense coverage, which reduced Cl⁻ adsorption by nearly 5-fold. The novel anionic synergy endow superior corrosion protection for the electrode, and is expected to promote the practical application of saline water electrolysis.     

Determination of Riboflavin Using Flow Injection Inhibitory Chemiluminescence

ABSTRACT

A new flow injection method for the determination of riboflavin based on the inhibition of the intensity of chemiluminescence (CL) from the luminol-K₃Fe(CN)₆ system is described. While riboflavin mixed with K₃Fe(CN)₆, by the fast oxidation reaction between riboflavin and K₃Fe(CN)₆, K₄Fe(CN)₆ was generated, which then inhibited the CL reaction of K₃Fe(CN)₆ and luminol in alkaline aqueous solution. The CL emission was correlated with the riboflavin concentration in the range from 0.032 to 100 μg·ml?¹, and the detection limit was 0.01 μg·ml?¹ (3σ). A complete analysis could be performed in 2 min with a relative standard deviation of less than 2.2%. The influence of foreign species was studied and the method has been applied successfully to the determination of riboflavin in pharmaceutical samples, the recovery was from 98.0% to 102%.     

The formation of an antitubercular complex [Fe(CN)5(INH)]3− through mercury(II)‐catalyzed ligand substitution reaction: A kinetic and mechanistic study

The kinetics and mechanism of the formation of an antitubercular complex [Fe(CN)₅(INH)]^3? based on the substitution reaction between K₄[Fe(CN)₆] and isoniazid (INH), i.e., isonicotinohydrazide, catalyzed by Hg²⁺ in aqueous medium was studied spectrophotometrically at 435 nm (the λ_max of the golden‐yellow‐colored complex [Fe(CN)₅(INH)]^3?) as a function of pH, ionic strength, temperature, and the concentration of the reactants and the catalyst. The replacement of coordinated CN^? in [Fe(CN)₆]^4? was facilitated by incoming ligand INH under the optimized reaction conditions: pH 3.5 ± 0.02, temperature = 30.0 ± 0.1°C, and ionic strength I = 0.05 M (KNO₃). The stoichiometry of the reaction and the stability constant of the complex ([Fe(CN)₅(INH)]^3?) have been established as 1:1 and 2.10 × 10³ M, respectively. The rate of catalyzed reaction was found to be slow at low pH values, to increase with increasing pH, to attain a maximum value at 3.50 ± 0.02, and finally to decrease after pH > 3.5 due to less availability of H⁺ ions needed to regenerate the catalytic species. The initial rates were evaluated for each variation from the absorbance versus time curves. The reaction was found to be pseudo‐first order with respect to [INH] and first order with respect to [Fe(CN)₆^4?] at lower concentration, whereas it was found to be fractional order at higher [INH] and [Fe(CN)₆^4?]. The ionic strength dependence study showed a negative salt effect on the rate of the reaction. Based on experimental results, a mechanism for the studied reaction is proposed. The rate equation derived from this mechanism explains all the experimental observations. The evaluated values of activation parameters for the catalyzed reaction suggest an interchange dissociative (I_d) mechanism. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 398–406, 2012     

The Effect of Ionic Liquid Covalent Bonding to Sol‐Gel Processed Film on Ion Accumulation and Transfer

Accumulation of electroactive anions into a silicate film with covalently bonded room temperature ionic liquid film deposited on an indium tin oxide electrode was studied and compared with an electrode modified with an unconfined room temperature ionic liquid. A thin film containing imidazolium cationic groups was obtained by sol‐gel processing of the ionic liquid precursor 1‐methyl‐3‐(3‐trimethoxysilylpropyl)imidazolium bis(trifluoromethylsulfonyl)imide together with tetramethylorthosilicate on the electrode surface. Profilometry shows that the obtained film is not smooth and its approximate thickness is above 1 μm. It is to some extent permeable for a neutral redox probe – 1,1′‐ferrocene dimethanol. However, it acts as a sponge for electroactive ions like Fe(CN)₆^3?, Fe(CN)₆^4? and IrCl₆^3?. This effect can be traced by cyclic voltammetry down to a concentration equal to 10^?7 mol dm^?3. Some accumulation of the redox active ions also occurs at the electrode modified with the ionic liquid precursor, but the voltammetric signal is significantly smaller compare with the bare electrode. The electrochemical oxidation of the redox liquid t‐butyloferrocene deposited on silicate confined ionic liquid film is followed by the expulsion of the electrogenerated cation into an aqueous solution. On the other hand, the voltammetry obtained with the electrode modified with t‐butyloferrocene solution in the ionic liquid precursor exhibits anion sensitive voltammetry. This is explained by anion insertion into the unconfined ionic liquid deposit following t‐butylferricinium cation formation.     

Noncovalent Immobilization of Molecular Electrocatalysts for Chemical Synthesis: Efficient Electrochemical Alcohol Oxidation with a Pyrene–TEMPO Conjugate

Electrocatalytic methods for organic synthesis could offer sustainable alternatives to traditional redox reactions, but strategies are needed to enhance the performance of molecular catalysts designed for this purpose. The synthesis of a pyrene‐tethered TEMPO derivative (TEMPO=2,2,6,6‐tetramethylpiperidinyl‐N ‐oxyl) is described, which undergoes facile in situ noncovalent immobilization onto a carbon cloth electrode. Cyclic voltammetry and controlled potential electrolysis studies demonstrate that the immobilized catalyst exhibits much higher activity relative to 4‐acetamido–TEMPO, an electronically similar homogeneous catalyst. In preparative electrolysis experiments with a series of alcohol substrates and the immobilized catalyst, turnover numbers and frequencies approach 2 000 and 4 000 h⁻¹, respectively. The synthetic utility of the method is further demonstrated in the oxidation of a sterically hindered hydroxymethylpyrimidine precursor to the blockbuster drug, rosuvastatin.     

Potassium bis(ethylenediamine)­copper(II) ferricyanide

The title compound, potassium bis(ethylenediamine‐N,N′)copper(II) hexacyanoferrate(III), K[Cu(C₂H₈N₂)₂]‐[Fe(CN)₆], contains [Cu(en)₂]²⁺ and [Fe(CN)₆]^3? complex ions, where en is ethylenediamine. The Fe^III and K⁺ ions lie on twofold axes and the Cu^II atom lies on an inversion center. The [Cu(en)₂]²⁺ ion has square‐planar coordination with a mean Cu—N distance of 1.992 (2) Å and the [Fe(CN)₆]^3? ion has distorted octahedral coordination with a mean Fe—C distance of 1.947 (2) Å.     

One-Pot Synthesis of Heterobimetallic Metal–Organic Frameworks (MOFs) for Multifunctional Catalysis

A one-pot synthesis of bimetallic metal–organic frameworks (Co/Fe-MOFs) was achieved by treating stoichiometric amounts of Fe and Co salts with 2-aminoterephthalic acid (NH₂-BDC). Monometallic Fe (catalyst A) and Co (catalyst F) were also prepared along with mixed-metal Fe/Co catalysts (B–E) by changing the Fe/Co ratio. For mixed-metal catalysts (B–E) SEM energy-dispersive X-ray (EDX) analysis confirmed the incorporation of both Fe and Co in the catalysts. However, a spindle-shaped morphology, typically known for the Fe-MIL-88B structure and confirmed by PXRD analysis, was only observed for catalysts A–D. To test the catalytic potential of mixed-metal MOFs, reduction of nitroarenes was selected as a benchmark reaction. Incorporation of Co enhanced the activity of the catalysts compared with the parent NH₂-BDC-Fe catalyst. These MOFs were also tested as electrocatalysts for the oxygen evolution reaction (OER) and the best activity was exhibited by mixed-metal Fe/Co-MOF (Fe/Co batch ratio=1). The catalyst provided a current density of 10 mA cm⁻² at 410 mV overpotential, which is comparable to the benchmark OER catalyst (i.e., RuO₂). Moreover, it showed long-term stability in 1 m KOH. In a third catalytic test, dehydrogenation of sodium borohydride showed high activity (turnover frequency=87 min⁻¹) and hydrogen generation rate (67 L min⁻¹ g⁻¹ catalyst). This is the first example of the synthesis of bimetallic MOFs as multifunctional catalysts particularly for catalytic reduction of nitroarenes and dehydrogenation reactions.     

Hydrogenation of the ansa-Chain of Rifamycins. X-ray crystal structure of (16S)-16,17,18,19-tetrahydrorifamycin S

The catalytic hydrogenation of rifamycin S ( 2 ) over Pd/C, followed by oxidation with K₃[Fe(CN)₆], generates a pair of 16,17,18,19-tetrahydrorifamycins S ( 3/4 ), epimeric at C (16). The use of PtO₂ as catalyst leads to the hydrogenation also of the C(28)?C(29) bond giving, after oxidation by K₃[Fe(CN)₆], a mixture of the epimers (16R)- and (16S)-16,17,18,19,28,29-hexahydrorifamycins S ( 5/6 ). Furthermore, we synthesized the (16R)- and (16S)-3-bromo derivatives 7/8 and (16R)- and (16S)-3-(piperidin-1-yl) derivatives 9/10 . The determination of the X-ray crystal structure of the most abundant epimer 4 of the tetrahydrorifamycins allowed the assignment of the absolute configuration at C(16) of all derivative. A Structure-activity relationship study showed that in general the (16R)-epimers are more potent inhibitors of bacterial RNA polymerase than the (16S)-epimers.     

Resonance Scattering Spectral Determination of HSA with a New Scattering Enhanced Reagent of K_3[Fe(CN)_6]

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