Chemiluminescent stages of Belousov-Zhabotinskii reactions in systems with ruthenium complexes

The autooscillatory catalytic oxidation of malonic acid (MA) by bromate (the Belousov-Zhabotinskii reaction) in the presence of the trisbipyridyl complexes of ruthenium Ru(II, III) is accompanied by bright chemiluminescence (CL) which appears during the reduction of the Ru(III) by the active intermediate products (organic radicals). It was shown that the chemiluminescence results from interaction of the Ru(III) not with MA radicals formed at the first stage of its oxidation but with stronger reducing agents, i.e., the radicals of hydroxymalonic acid and, probably, the OCOOH and HO₂ radicals. The main paths leading to the formation and consumption of these radicals are reactions involving the bromate. A simplified scheme is presented for the process leading to the appearance of chemiluminescence in the MABrO₃ ^–-Ce(III, III) and MA-BrO₃ ^–-Ce(III, IV)-Ru(II, III) systems. It confirms the experimental relatinships between the maximum intensity of the chemiluminescence and the concentrations of the reagents.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 5, pp. 566–573, September–October, 1990.     

Synthetic and kinetic studies on copper(II), nickel(II) and cobalt(III) complexes of 1,4,7,10,13-pentaazacyclohexadecane ([16]aneN5)

Summary The pentadentate macrocycle 1,4,7,10,13-penta-azacyclo-hexadecane [16]aneN₅=(3)=L} has been prepared and a variety of copper(II), nickel(II) and cobalt(III) complexes of the ligand characterised. The copper complex [CuL](ClO₄)₂, on the basis of its d-d spectrum, appears to be square pyramidal, while [NiL(H₂O)](ClO₄)₂ is octahedral. The copper(II) and nickel(II) complexes dissociate readily in acidic solution and these reactions have been studied kinetically. For the copper(II) complex, rate=k_H[complex][H⁺]² with k_H =4.8 dm⁶ mol^–2s^–1 at 25 °C and I=1.0 mol dm^–3 (NaClO₄) with H=43 kJ mol^–1 and S ₂₉₈ =–89 JK^–1 mol^–1. Dissociation rates of the copper(II) complexes increase with ring size in the order: [15]aneN₅ < [16]aneN₅ < [17]aneN₅. For the dissociation of the nickel(II) complex, rate=k_H[Complex][H⁺] with k_H=9.4×10^–3 dm³mol^–1 s^–1 at 25 °C and I =1.0 mol dm^–3 (NaClO₄) with H=71 kJ mol^–1 and S ₂₉₈ =–47 JK^–1mol^–1.The cobalt(III) complexes, [CoLCl](ClO₄)₂, [CoL(H₂O)]-(ClO₄)₃, [CoL(NO₂)](ClO₄)₂, [CoL(DMF)](ClO₄)₃ (DMF=dimethylformamide) and [CoL(O₂CH)](ClO₄)₂ have been characterised. The chloropentamine [CoCl([16]aneN₅)]²⁺ undergoes rapid base hydrolysis with k_OH=1.1× 10⁵dm³ mol^–1s^–1 at 25°C and I=0.1 mol dm^–3 (H=73 kJ mol^–1 and S ₂₉₈ =98 JK^–1 mol^–1). Rapid base hydrolysis of [CoL(NO₂)]²⁺ is also observed and the origins of these effects are considered in detail.     

Metal chelates of heterocyclic nitrogen containing ketones,XIII. Cobalt(II), nickel(II) and palladium(II) complexes of 2-picolyl- and 2-lutidyl-methyl ketones

Summary The preparation and characterization of a series of new coordination compounds of cobalt(II), nickel(II) and palladium(II) containing 2-picolyl- or 2-lutidyl-methyl ketone (HPMK or HLMK) and various anions, Cl^–, Br^–, NO ₃ ^– , NCS^– or BF ₄ ^– , are reported. Complexes of square planar, tetrahedral and octahedral stereochemistry as well as five-coordinate species were isolated. The reaction products were found to be dependent on the molar ratios, pH and the temperature at which the reaction takes place. Cobalt(II) thiocyanate was found to form a complex of the type [CoL₃][Co(NCS)₄] (L = HPMK or HLMK). Also complexes containing coordinated BF₄ were isolated. The ligand field parameters (Dq, B and ) for the cobalt(II) and nickel(II) complexes were calculated using the averaged-ligand-field approximation. The influence of the substituents of theses parameters and on the stereochemistry are discussed.     

Studies on the kinetics and mechanism of dissociation of copper(II) and nickel(II) complexes of the macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene in perchloric acid media

Summary Acid catalysed dissociation of the copper(II) and nickel(II) complexes (ML²⁺ of the quadridentate macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene (L) has been studied spectrophotometrically. Both complexes dissociate quite slowly with the observed pseudo-first order rate constants (k_obs) showing acid dependence; for the nickel(II) complex (k_obs)=k_O+k_H[H⁺], the k_o path is however absent with the copper(II) complex. At 60°C (I=0.1M) the k_H values areca 10^–4 M^–1 s^–1 for both complexes; k _H ^Cu /k _H ^Ni =ca. 3.9, comparable to some other square-planar complexes of these metal ions. The rate difference is primarily due to H values [copper(II) complex, 29.4±0.5 kJ mol^–1; nickel(II) complex, 35.6±1.5 kJ mol^–1] with highly negative S values [for copper(II), –215.5 ±6.1 JK^–1 mol^–1 and for nickel(II), –208.1 ±5.6 JK^–1 mol^–1] which are much higher than the entropy of solvation of Ni²⁺ (ca. –160 JK^–1 mol^–1) and Cu²⁺ (ca. –99 JK^–1 mol^–1) ions; significant solvation of the released metal ions and the ligand is indicated.     

Studies on transition-metal nitrido and oxo complexes. Part VII(1). Substituted nitrido complexes of osmium and ruthenium

Summary Addition reactions of [MNCl₄]^– (M = Os or Ru) with ligands L or L to give [MNCl₄ · L]^– or [(MNCl₄)₂L]^2– (L = pyridine, pyridine-N-oxide,iso-quinoline or DMSO; L = hexamethylenetetramine, pyrazine or dioxan) are described. With NCO^–, [OsNCl₅]^– gives [OsN(NCO)₅]^2– but NCS^– gives a thionitrosyl complex, [Os(NS)(NCS)₅]^2–. Reactions of OsNCl₃(AsPh₃)₂ with pyridine, 1,10-phenanthroline and tertiary phosphites and phosphinites have been studied, as have reactions of triphenylphosphine with OsOCl₄ andtrans- [MO₂Cl₄]^2– (M = Os or Ru). The nitrido-iodo complexes [OsNI₄]^– and OsNI₃, (SbPh₃)₂ are also reported.     

Synthesis and characteristics of the redox behavior of a ditopic compound contaiing tetraaza macrocyclic and crown ether fragments

A new ditopic compound has been obtained from monocyclic fragments by the reaction of formylbenzo-15-crown-5 with a macrocyclic complex of nickel(II) that contains a pendant amino group and it is characterized by methods of electron and IR spectroscopy, FAB mass spectrometry, and cyclic voltammetry. It was established that binding of protonated amines (methylamine, -alanine) to crown ether receptor centers causes a cathodic shift of the redox potential (by 100–160 mV) of the Ni^IIIL/ Ni^IIL pair of the ditopic complex. Ditopic and monocyclic complexes of nickel(III) were prepared by preparative electrolysis in acetonitrile solutions. The kinetics of the reduction of nickel(III) by bifunctional substrates capable of binding with the crown ether was investigated. The rate of reduction of Ni(III) in the reaction with m-aminophenol in the ditopic complex is 50 times less than in the monocyclic complex and 6 times greater in the reaction with -alanine hydrazide.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 2, pp. 162–167, March–April, 1992.     

Photoreduction of nitrobenzene to aniline in “hybrid” photocatalytic systems

Irradiation of suspensions of CdS in water-ethanol mixtures containing nibrobenzene with light at > 320 run does not in practical terms lead to the reduction of the nitrobenzene to aniline. It has been shown that the formation of aniline occurs when solvato complexes of vanadium(III) (PhNH₂=18.1·10^–3) and vanadium(IV) (PhNH₂= 2.84·10^–3) are added to the system. The photocatalytic reduction of nitrobenzene is accompanied by oxidation of the alcohol to acetaldehyde and acetal. The proposed process mechanism includes stages and acceptance of an electron photogenerated in the semiconductor by vanadium compounds and of a hole by molecules of the alcohol and subsequent stages of reaction of the reduced forms of vanadium, and also of the ethoxy radicals with nitrobenzene, which leads to its reduction.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 5, pp. 550–557, September–October, 1989.     

Photochemical properties of peroxo complexes of titanium,intermediate products in the photocatalytic liquid-phase oxidation of alcohols

A study has been made of the photochemical reactions of titanium(IV) peroxo complexes formed in the reaction of titanium tetrachloride with hydrogen peroxide in alcoholic solutions and which are characterized by intense charge transfer bands at 360–425 nm. Irradiation of the solutions with light of = 254 nm leads to the decomposition of the titanium(IV) peroxo complexes, the formation of titanium(III) compounds, as well as the oxidation of the alcohol to aldehyde. In the irradiated frozen solutions associated complexes of titanium(III), organic free radicals formed from the alcohol molecule, as well as peroxy radicals have been identified by EPR. Irradiation with light corresponding to the longwave band of the peroxo complexes leads to their decomposition but titanium(III) compounds and alcohol oxidation products are not formed in this case. In irradiated frozen solutions the formation of paramagnetic titanium(IV) complexes containing the fragment Ti...O ₂ has been established, as well as other paramagnetic particles identified tentatively as coordinated Ti...O ₂ ^· radicals or radical pairs. It is shown that the decomposition of hydrogen peroxide in the presence of titanium(IV) compounds is photocatalytic.Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 24, No. 1, pp. 67–74, January–February, 1988.     

Influence of added water on pathways and efficiency of photocatalytic reactions in ethanol solutions of titanium tetrachloride

Electronic spectroscopy, ESR, and gas-liquid chromatography have been used in studying the action of light with =254 nm on ethanol-water solutions of titanium tetrachloride. It has been established that, in the course of irradiation, a photocatalytic process develops with the participation of coordination compounds of titanium(IV) and (III), resulting in oxidation and breakdown of the ethanol to form acetaldehyde, methane, ethane, ethyl chloride, and molecular hydrogen. In the presence of small amounts of added water (up to 0.5 M), the efficiency of CH₄ and C₂H₇ formation is much lower but the yield of H₂ is higher, in comparison with the yields of these products in absolute ethanol. With further increases in the water concentration, the rates of formation of methane, ethane, and acetaldehyde increase. The maximum quantum yields () are as follows: (CH₄)=1.8 · 10^–4 and (C₂H₆)=1 · 10^–3 in absolute ethanol; (CH₃CHO)= 1.6·10^–2 in ethanol with the addition of 6.0 M H₂O; (H₂)=6.7·10^–3 in solutions containing 0.5 M H₂O. The observed differences in the product yields are explained by a change in the composition and structure of the titanium compounds that act as the photocatalyst, a change that takes place when the water concentration is varied. A mechanism is proposed for these reactions.Translated from Teoreticheskaya i Éksperimentai'naya Khimiya, Vol. 22, No. 1, pp. 51–58, January–February, 1986.     

Flow-Injection Methods for Determining Europium in Mixtures of Lanthanides(III)

Possible approaches to the flow-injection determination of europium(III) in the presence of other lanthanides are studied. One of the approaches is based on the direct amperometric detection of europium(III) in a flow-injection system with a glassy-carbon electrode at a potential of –0.85 V (against a saturated calomel electrode). The linear calibration range is 5.0 × 10^–5–5.0 × 10^–4M of europium, and the limit of detection is 1.8 × 10^–5M (2.8 g/mL). The throughput capacity is 90 h^–1for a sample volume of 600 L. Another approach involves the online reduction of europium(III) to europium(II) in a flow Jones mini-reductor filled with amalgamated zinc, followed by the spectrophotometric detection of europium(II) using redox reactions between europium(II) and iron(III) in the presence of 1,10-phenanthroline, molybdophosphoric acid, or Methylene Blue. In the latter case, the calibration curve is linear in the range 0–5.0 × 10^–6M europium(III), the limit of detection is 9.0 × 10^–8M (0.014 g/mL). The throughput capacity is 180 h^–1for a sample volume of 200 L. The performance parameters of the proposed flow-injection methods are estimated using the analysis of artificial mixtures and dissolved samples of samarium(III) oxide and lanthanum(III) fluoride containing europium impurities as an example.     

A new convenient method for the synthesis of mixed-ligand β-diketonato Tc(III) complexes

A new convenient method has been proposed to synthesize mixed-ligand -diketonato Tc(III) complexes, using the ligand exchange reaction [Tc(acac)₂(CH₃CN)₂]⁺+L^–[Tc(acac)₂L]+ +2CH₃CN where L is bza, dpm or dbm. The yield was about 30–40%. UV-visible and IR spectra of these complexes were measured. Characteristic features of the compounds were compared with those of the corresponding complexes of ruthenium.     

A selective and sensitive spot-test for gold

Summary A new spot test for gold has been developed, based on the oxidation of colourless phenolphthalin to red phenolphthalein in alkaline medium. The sensitivity is 0.2g of gold on a spot-plate and 0.15g on filter paper. Ce(IV) interferes seriously, and Pt(IV) at high concentrations, but Pd(II), Cu(II), Fe(III), Cr(III), Ni(II), UO₂(II), ClO₄ ^–, CrO₄ ^2–, BrO₃ ^–, IO₃ ^–, MoO₄ ^2–, and WO₄ ^2– do not.

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Zusammenfassung Eine neue Tüpfelreaktion für Gold wurde entwickelt, die auf der Oxydation des farblosen Phenolphthalins zu rotem Phenolphthalein in alkalischem Milieu beruht. Die Empfindlichkeit beträgt auf der Tüpfelplatte 0,2g Gold, auf Filterpapier 0,15g. Cer(IV) stört stark, Pt(IV) in hoher Konzentration; hingegen stören Pd(II), Cu(II), Fe(III), Cr(III), Ni(II), UO₂(II), ClO₄ ^–, CrO₄ ^2–, BrO₃ ^–, JO₃ ^–, MoO₄ ^2– und WO₄ ^2– nicht.

     

Anodic Processes Involving Trifluoromethyl Cobaloxime and Nucleophiles

Anodic oxidation of trifluoromethyl cobaloxime (CF₃)Co(DH)₂Py in the presence of such nucleophiles as pyridine or NO^– ₃ and C₆F₁₃COO^– anions is studied. A controlled-potential electrolysis and ¹⁹F NMR spectroscopy show the anodic reaction products to contain compounds with the bond >N–CF₃. A mechanism for the reaction between a labile Co(+4) complex and pyridine is offered. At potentials more positive than that of the Co(+3) Co(+4) oxidation, secondary products of electrochemical reaction form and are revealed by a cathodic reduction peak.     

Simultaneous flow injection speciation of iron(II) and iron(III) cyano complexes utilizing electrochemical and atomic absorption detectors in series

Summary A method is described for the simultaneous speciation of Fe(CN) ₆ ^4– and Fe(CN) ₆ ^3– in a flow injection (FIA) system comprising electrochemical (EC) and flame atomic absorption spectrometry (AAS) detectors in series. One of these species is detected amperometrically at a Pt-electrode by applying the required potential and measuring the resulting reduction or oxidation current of the appropriate iron cyanide complex. Total iron in both species is determined by an AAS detector. The EC detector is inherently more sensitive, with a detection limit of 0.5 g Fe l^–1 and a relative standard deviation of 1.0% for a 0.040 g Fe ml^–1 sample. The limit of detection for the AAS detector is 0.5 g Fe ml^–1, and the relative standard deviation for a 5.70 g Fe ml^–1 sample is 0.40%. The method enables up to 60 analyses (120 speciations) per hour and obviates the problem of easy oxidation of Fe(CN) ₆ ^4– .

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Simultane Speziation von Eisen(II)- und Eisen(III)-Cyanokomplexen durch Flie\injektionsanalyse mit Hilfe von hintereinander geschalteten elektrochemischen und AAS-Detektoren

     

Kinetics and mechanism of complex formation between O-bonded cis-(diglycinato)bis(ethylenediamine)cobalt(III) and α-cis-(diglycinato) (triethylenetetramine)cobalt(III) with nickel(II) in aqueous medium

Summary The kinetics of reversible complexation of Ni(OH₂) _inf6 ^sup2+ with oxygen-bonded glycinatocobalt(III) substrates N₄-Co(glyH)gly²⁺ [N₄ = (en)₂ or trien; glyH = H₃N⁺CH₂-COO^–] have been investigated by the stopped-flow technique in the 20–35° C range, at pH = 6.08–6.82 and I = 0.3 mol dm^–3. The formation of N₄Co(glyH)glyNi⁴⁺ occurred via the reaction of Ni(OH₂) _inf6 ^sup2+ with the deprotonated form of the cobalt(III) substrates, N₄Co-(glyH)gly²⁺. The rate and activation parameters for the formation and dissociation of the binuclear species are reported. The formation rate constants k _f (at 25° C), activation enthalpy and entropy H , S for N₄Co-(glyH)glyNi⁴⁺ are 320±49, 341 ± 52dm³mol^–1 s^–1, 78 ± 7, 79 ± 5 kJmol^–1 and 64 ± 24, 69 ± 18 JK^–1 mol^–1 for the ethylenediamine and triethylenetetraminecobalt(III) substrates, respectively. This result indicates that the rate and activation parameters are virtually independent of the nature of N₄ moities, which strongly suggests that the formation of mono-bonded species occurs via entry of one of the pendant NH₂ groups into the coordination sphere of nickel(II) via a rate-limiting Ni-OH₂ bond dissociation mechanism (I_d). The binuclear species exist in dynamic equilibrium between the monodentate and chelated forms, with the chelate form predominating. The low values of spontaneous dissociation rate constant for the binuclear species (k _r- 0.095^–1 at 25° C) in comparison with the high values of dissociation rate constants of monodentate nickel(II) complexes reported in the literature also support the chelate nature of the binuclear species.     

On the linear mixed valence compounds obtained by partial oxidation ofcis-diamminedichloroplatinum(II)

Summary The partial oxidation products ofcis-[Pt(NH₃)₂Cl₂] (Cisplatin) by (NH₄)₂S₂O₈ and by K₂PtCl₆, as well as the recrystallization of the former product in various solutions (HClO₄, NaClO₄, NaBF₄, NaHSO₄, H₂SO₄) have been re-examined. Contrary to the conclusions of previous works, the general formulation of these compounds iscis-[Pt²⁺(NH₃)₂Cl₂]X_x·yH₂O ( = 0.3–0.4, X = SO ₄ ^2– , PtCl ₄ ^2– , ClO ₄ ^2– , BF ₄ ^2– , HSO ₄ ^2– , ..., 0y 1). These materials are all linear chain Pt—Pt compounds belonging to the class III of Robin-Day compounds with Pt—Pt distances in the range 3.00–3.06 Å. The oxidation of Cisplatin by persulphate gives two sulphate compounds of the same formulation (x = 0.2), which differ in aspect, metallic character and spectral properties. Structural information was obtained from polarized micro-Raman spectra of a needle-like sample of the perchlorate and from X-ray powder diffraction spectra. The cell of the perchlorate was orthorhombic while the two sulphate forms had a monoclinic cell with slightly different parameters. Expansion of the Cisplatin interchain distance occurred only along one crystallographic direction. The two sulphate forms differed in the degree of order along this direction. An approximate structure is proposed and discussed in relation to the Cisplatin precursor.     

Chemistry of μ-hydridobis[pentacarbonylchromium(0)] species. Part III. Redox reactions with mercury(II) compounds and iodine

Summary [Cr₂(CO)₁₀(-H)]^– undergoes ready hydride substitution on reaction with HgX₂ (X = Cl, Br, I or SCN) or with iodine in acetone, yielding [Cr₂(CO)₁₀(-X)]^– complex species which can be converted quantitatively into [Cr(CO)₅X]^– anions by reactions conducted in the presence of an excess of X^–.LCr(CO)₅ and (L-L)Cr(CO)₄ complexes (L = pyridine; L-L = 1,10-phenanthroline or 2,2-bipyridine) are easily prepared by reactions performed in the presence of the L or L-L ligand, respectively.     

Electronic and ESR spectroscopic study of thiocyanate-containing coordination compounds of titanium(III) in alcohol solutions

In an investigation of electronic and ESR spectra, it has been established that titanium(III) with the thiocyanate ion (in ethanol) forms distorted tetrahedral and octahedral complexes. The tetrahedral compounds, which are hydroxo complexes of titanium(III) that contain one hydroxyl group and three thiocyanate ions in the coordination sphere, give signals in the ESR spectra with g_o=1.960, A_o=15.0·10^–4 cm^–1 g=1.958, A ^Ti =26.4·10^–4cm^–1, g= 1.691, A^Ti=9.0·10^–4 cm^–1. In the ESR spectra of liquid solutions, additional splitting on the nitrogen atoms is manifested(A _o ^N =2.2·10^–4 cm^–1), which indicates bonding of thiocyanate ions through the nitrogen atom. The pseudo-octahedral complexes of titanium(III), containing from two to six thiocyanate ions in the coordination sphere, are characterized by d-d absorption bands in the 520–590 nm region; and at 77°K, they give anisotropic ESR signals. On the basis of the temperature dependences of the equilibrium constants for the reaction of conversion of the tetrahedral complexes to the octahedral complexes, and also the lifetimes of the tetrahedral complexes, values have been estimated for the heat of reaction (H=26.8 kJ/mole) and the entropy change (S=–1.66 kJ/mole·°K) of the equilibrium process, and also the activation energy for the reaction of titanium(III) thiocyanate formation (E=37 kJ/mole).Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 560–567, September–October, 1985.     

Outer-sphere electron-transfer reactions with the participation of platinum(IV) haloammines

The kinetics of some outer-sphere electron-transfer reactions with the participation of the complexes [Pt(NH₃)_nX_6–n]² (n=6–0, X=Cl^–, Br^–) and dipyridyl complexes of Os(II), Ru(II), Ir(III), and Cr(II) have been investigated by means of luminescence-quenching measurements and flash photolysis. Estimates of the values of the Pt(IV)/Pt(III) one-electron potential and the change in the free energy of activation of electron self-exchange processes of the type Pt(IV) Pt(III) have been obtained on the basis of an analysis of the dependence of the rate constant on the change in the free energy accompanying the electrontransfer process.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 4, pp. 455–462, July–August, 1990.     

Mechanism and kinetics of the reduction of In(III) ions at a polycrystalline gold electrode from highly concentrated ZnCl2 solutions

Summary The mechanism of the cathodic reduction of In(III) at gold has been studied by rotating disc and ring-disc voltammetry in highly concentrated aqueous ZnCl₂ solutions. At concentration of the base electrolyte higher than 7 mol dm^–3, the voltammetric curves recorded at the disc electrode split into two well-separated waves which correspond to the successive charge transfer reactions: In(III) + 2e^– In(I) and In(I) + e^– In. By the use of coulometric and potentiometric techniques, the formal potentials of the In(III)/In(I), In(III)/In and In(I)/In redox couples as well as the equilibrium constants of the reproportionation reaction In(III) + 2 In 3 In(I) has been determined and discussed. The kinetic parameters of the In(III)/In(I) electrode reaction have been also evaluated and discussed.

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Mechanismus und Kinetik der Reduktion von In(III)-Ionen an der Goldelektrode in hochkonzentrierten wäßrigen ZnCl₂-Lösungen

Zusammenfassung Es wird der Mechanismus der Reduktion von In(III)-Ionen in hochkonzentrierten ZnCl₂ Lösungen mittels der Scheiben- und Ring-Scheiben-Elektrode aus Gold untersucht. Wenn die Konzentration des Grundelektrolyten 7 mol dm^–3 übersteigt, verteilen sich die erhaltenen Stromspannungskurven auf zwei gut gestaltete Stufen, die den konsekutiven Durchtrittsreaktionen In(III) + 2e^– In(I) und In(I) + e^– In entsprechen. Aufgrund der coulometrischen und potentiometrischen Messungen werden die Formal-Standardpotentiale der In(III)/In(I)-, In(III)/In-und In(I)/In-Redoxpaare, die Gleichgewichtskonstanten der Reproportionierungsreaktion In(III) + 2 In 3 In ermittelt. Die kinetischen Parameter der Durchtrittsreaktion In(III)/In(I) werden bestimmt und diskutiert.