Behaviour of a chalcocite copper ion-selective electrode in solutions of iron(III) ions

The effect of iron(III) ions on the potential of the chalcocite electrode was investigated. Linear graphs were obtained for pFe(III) = 2-4, and were suitable for analytical purposes. The effect of ligands complexing iron(III) was studied, and the potential shown to be due to the concentration of free iron(III) ions only. The pH effect is mainly connected with solution reactions. A mechanism of potential response, based on a redox reaction, has been postulated, but the response does not depend on the redox potential in the bulk of the solution.     

Redox reactions of ferricyanide ions in layer-by-layer deposited polysaccharide films: a significant effect of the type of polycation in the films

Redox reactions of ferricyanide ions, [Fe(CN)6]3-, in polysaccharide thin films that were prepared by layer-by-layer (LbL) deposition on the surface of a gold electrode were studied electrochemically by cyclic voltammetry. LbL films composed of alginic acid (AGA) and carboxymethylcellulose (CMC) were successfully prepared using poly(ethyleneimine) (PEI) and poly(diallyldimethylammonium chloride) (PDDA) as the cationic counterparts in the electrostatic LbL deposition. The deposition behavior of the PEI-based films significantly depended on the pH of the solutions from which the LbL films were deposited, while the effects of pH were negligibly small for the PDDA-based films due to the pH-independent positive charges on the PDDA chains. The cyclic voltammograms (CVs) of [Fe(CN)6]3- ions on the LbL film-coated electrodes revealed that all the LbL films tested are permeable to [Fe(CN)6]3- ions and that the redox reactions of [Fe(CN)6]3- ions proceed smoothly in the LbL polysaccharide films. It was found that [Fe(CN)6]3- ions are concentrated in the films from the bulk solution, depending on the pH of the medium and on the type of polycations in the film. The PEI-based films concentrated [Fe(CN)6]3- ions more effectively in an acidic solution than in neutral and basic media, while the pH effect was not observed for the PDDA-based films. In addition, we found that the [Fe(CN)6]3- ions are confined in the LbL films due to a strong binding of the ions to the positively charged sites arising from the protonated amino groups in the films. The confined [Fe(CN)6]3- ions exhibited redox reactions in the films, with the redox potentials being shifted to the positive or negative direction in the PEI- or PDDA-based film, respectively, as compared to the redox potential of diffusing [Fe(CN)6]3- ions. Thus, significant effects of the type of polycation in the LbL films on the redox reactions of [Fe(CN)6]3- ions were observed.     

Bis(Iminophosphorano)-Substituted Pyridinium Ions and their Corresponding Bispyridinylidene Organic Electron Donors

Optimized synthetic procedures for pyridinium ions featuring iminophosphorano (−N=PR₃; R=Ph, Cy) π-donor substituents in the 2- and 4- positions are described. Crystallographic and theoretical studies reveal that the strongly donating substituents severely polarize the π-electrons of the pyridyl ring at the expense of aromaticity. Moreover, the pyridinium ions are readily deprotonated to generate powerful bispyridinylidene (BPY) organic electron donors. Electrochemical studies show exceptionally low redox potentials for the two-electron BPY/BPY²⁺ couples, ranging from −1.71 V vs the saturated calomel electrode for 3PhPh (with four Ph₃P=N− groups) to −1.85 V for 3CyCy (with four Cy₃P=N− groups). These new compounds represent the most reducing neutral organic electron donors (OEDs) currently known. Some preliminary reductions involving 3CyCy showed enhanced capability owing to its low redox potential, such as the thermally activated reduction of an aryl chloride, but purification challenges were often encountered.     

Synthesis, structure, spectroscopy and redox chemistry of square-planar nickel(II) complexes with tetradentate o-phenylenedioxamidates and related ligands

A series of four-coordinate square-planar nickel(II) complexes of o-phenylenebis(N'-methyloxamidate)(L1) and related o-phenylene(N'-methyloxamidate)oxamate (L2) and o-phenylenebis(oxamate)(L3) tetradentate ligands have been synthesized and characterized structurally, spectroscopically and electrochemically. The parent nickel(II)-L1 complex presents an intense MLCT band in the UV region (lambda max = 357 nm) and a distinctive 1 s --> 4p CT satellite in the Ni K-edge XANES spectrum (E = 8339.2 eV). These features together with the short Ni-N(amidate) bond lengths (1.85-1.93 A) as revealed by the analysis of the Ni K-edge EXAFS spectrum and confirmed by single-crystal X-ray diffraction are typical of square-planar low spin (S = 0) Ni(II) ions. The dianionic nickel(II) complexes, [Ni(II)L(i)](2-)(i = -3), experience two redox processes in acetonitrile at 25 degrees C. The first redox process, at moderately low potentials (E1 = 0.12-0.52 V vs. SCE), is a reversible one-electron metal-centered oxidation to the corresponding monoanionic nickel(III) complexes, [Ni(III)L(i)]-. The second redox process, at relatively high potentials (E2 = 0.86-1.04 V vs. SCE), is a quasireversible to irreversible one-electron oxidation largely centered on the o-benzenediamidate fragment of the non-innocent ligand, yielding the corresponding neutral nickel(iii) complexes with a o-benzosemiquinonediimine pi-cation radical ligand, [Ni(III)(L(i))*+]. The singly and doubly oxidized species of the parent nickel(II)-L1 complex have been prepared by chemical oxidation and characterized spectroscopically in acetonitrile at -40 degrees C. The stable singly oxidized nickel(III)-L1 species presents an intense LMCT band in the NIR region (lambda max = 910 nm) and a rhombic X-band EPR spectrum (g1 = 2.193, g2 = 2.080 and g3 = 2.006) characteristic of square-planar low spin (S = 1/2) Ni(III) ions. The unstable double oxidized nickel(III)-L1 pi-cation radical species exhibits a rather intense visible band (lambda max = 645 nm) that is tentatively assigned as a MLCT transition from the Ni(III)-benzosemiquinone type ground state to the Ni(IV) excited state.     

Cyclic transmembrane charge transport mediated by low-potential pyrylium ions

We have investigated the capacity of a series of N-dialkylaminophenyl-substituted pyrylium and thiopyrylium ions to act as photosensitizers and redox mediators between reactants separated by bilayer membranes. These studies were prompted by earlier results indicating that simple trimethy- and triphenyl-substituted analogues could promote efficient photosensitized transmembrane redox between vectorially organized reactants by an electroneutral e(-)/OH(-) antiport mechanism. Unlike the dyes used in the earlier studies, the ions investigated herein absorb strongly throughout the visible absorption region and are therefore potentially useful in solar photoconversion processes. We demonstrate that these ions can carry out cyclic electron transport between phase-separated electron donors and occluded Co(bpy)(3)(3+) in several transversely organized vesicles. The quantum yields obtained were relatively low, but were independent of the membrane microviscosity, suggesting that transmembrane diffusion was not rate-limiting. Triphenylpyrylium and triphenylthiopyrylium ions were shown to be capable of acting as combined photosensitizers/redox relays, apparently by direct oxidation of either solvent (water) or buffer (acetate) ions from their triplet-excited state. These reactions did not require addition of separate photosensitizers and electron donors; as such, they represent a minimal photochemical scheme for effecting transmembrane charge separation. The low-potential visible-absorbing pyrylium ions were unable to function in this dual capacity, consistent with thermodynamic limitations. However, redox titrations established that the pyranyl radicals of these dyes should be capable of reducing H(+) to H(2) in weakly acidic solutions. Consistent with their strongly reducing nature, these dyes were shown to be capable of forming methyl viologen radical in photoinitiated transmembrane redox reactions.     

Triorganostannylation of halo- and dihaloadamantanes and 5-chloro-2-adamantanone in liquid ammonia by the S(RN)1 mechanism. Relative reactivity of nucleophiles and bridgehead halides

The reactions of 1-bromo-, 1-iodo-, 2-bromo-, 1,3-dibromo-, and 1,4-dibromoadamantane with Me(3)Sn(-) ions were studied in liquid ammonia. The photostimulated reaction of 1-haloadamantane (1-XAd, X = Br, I) or 2-BrAd with Me(3)Sn(-) ions gave in a few minutes excellent yields of the substitution products. The 1,3-dibromo- and 1,4-dibromoadamantane with Me(3)Sn(-) ions also reacted very fast under irradiation to give the disubstitution product in good yields. In competition experiments, 1-ClAd is 5.3 times more reactive than 5-chloro-2-adamantanone (9) toward Me(3)Sn(-) ions in liquid ammonia. When the nucleophile is the Ph(2)P(-) ion, 1-ClAd reacts 2.4 times faster than 9. This is the first time that no redox catalysis was observed when the bridgehead compound bears a carbonyl group as a pi acceptor. On the other hand, the nucleophile Me(3)Sn(-) ion was ca. >1000 times more reactive than Ph(3)Sn(-) ions toward 1-adamantyl radicals, in contrast to the behavior of aryl radicals, where both nucleophiles have the same reactivity.     

Weak antiferromagnetic coupling for novel linear hexanuclear nickel(II) string complexes (Ni6 12+) and partial metal-metal bonds in their one-electron reduction products (Ni6 11+)

The preparation, crystal structures, magnetic properties and electrochemistry of novel linear hexanuclear nickel string complexes (Ni6(12+)) and their corresponding 1-e(-) reduction products (Ni6(11+)) are reported. In these complexes, the hexanickel chain is in a symmetrical arrangement (approximately D(4) symmetry) and is helically supported by four bpyany(2-) ligands [bpyany(2-) = the dianion of 2,7-bis(alpha-pyridylamino)-1,8-naphthyridine]. The Ni6(12+) complexes show that the two terminal nickel ions have high-spin states (S = 1) and the four inner ones have low-spin states (S = 0). The two terminal nickel ions exhibit weak antiferromagnetic coupling of ca.-5 cm(-1). All of Ni6(12+) complexes display three reversible redox couples at about -0.70, -0.20 and +1.10 V (vs. Ag/AgCl). The first reduction wave at about -0.20 V suggests facility of 1-e(-) reduction for the Ni(6)(12+) compounds. The reaction of Ni(6)(12+) complexes with hydrazine afforded the 1-e(-) reduction products (Ni6(11+)). As far as we are aware, the shortest bond distance of 2.202 A with a partial metal-metal bond was observed in Ni6(11+) compounds. The magnetic results of these Ni6(11+) compounds are in agreement with a localized model, in which the two terminal nickel ions are in a spin state of S = 1 whereas the central Ni3-Ni4 pair in a spin state of S = 1/2. The N6(11+) compounds show relatively strong antiferromagnetic coupling of about 60 cm(-1) between the terminal and the central dinickel ions.     

Defect chemistry, redox kinetics, and chemical diffusion of lithium deficient lithium niobate

High-temperature optical in situ spectroscopy was used to investigate the defect absorption, redox kinetics, and chemical diffusion of a lithium deficient (48.4 mol% Li(2)O) congruent melting lithium niobate single crystal (c-LN). Under reducing atmospheres of various oxygen activities, a(O(2)), UV-Vis-NIR spectra measured at 1000 °C are dominated by an absorption band due to free small polarons centered at about 0.93 eV. The polaron band intensity was found to follow a power law of the form a(O(2))(m) with m = -1/4. A chemical reduction model involving electrons localized on niobium ions on regular lattice sites can explain the observed defect absorption and its dependence on oxygen activity. The kinetics of reduction and oxidation processes upon oxygen activity jumps and the associated chemical diffusion coefficients are found in close agreement over a range from -0.70 to -14.70 in log a(O(2)), indicating a reversible redox process. Assuming coupled fluxes of lithium vacancies and free small polarons for the attainment of stoichiometry, the diffusion coefficients of lithium vacancies as well as of lithium ions in the lithium deficient c-LN have been determined at 1000 °C.     

Triple channel sensing of Pb(II) ions by a simple multiresponsive ferrocene receptor having a 1-deazapurine backbone

A new redox, chromogenic, and fluorescent chemosensor molecule based on a deazapurine ring selectively senses aqueous Pb2+ in acetonitrile over other metal ions examined: redox shift (DeltaE1/2 = 0.15 V of the Fe(II)/Fe(III) redox couple), the colorless to orange color change, and an emission change of 620-fold, with an unprecedented detection limit of 2.7 microg L-1. The signal transduction occurs via a reversible CHEF with this inherent quenching metal ion.     

Titrimetric determination of thiocyanate and thiosulphate ions by oxidation with iodine in alkaline solution

Thiocyanate (2.7-90 mug) and thiosulphate (4.5-90 mug) ions are oxidized by iodine in alkaline media to sulphate ions. After acidification, the excess of iodine is extracted into chloroform, and the iodide ions formed in the redox reaction subjected to an amplification reaction. Either a titrimetric or a spectrophotometric finish may be used. Each thiocyanate and thiosulphate ion results in the ultimate production of 19 and 24 iodine molecules, respectively.     

钙钛石型复合氧化物催化剂LaMn~yCo~1~-~yO~3催化性能的研究 Ⅱ. 过渡金属离子之间的相互作用与在氨氧化反应中的催化性能

发现钙钛石型复合氧化物LaMn~yCo~1~-~yO~3中B位过渡金属离子Mn,Co 之间的相互作用及其氧化还原性是影响氨氧化反应中NO选择的重要因素.B位少量掺杂可促进过渡金属离子的氧化还原性,但B位组成相当时(y=0.5),则不利于它们的氧化还原.富锰区(y>0.5),Mn^3^+-O^2^--Mn^4^+的超交换作用对样品的磁性及NO 选择性起决定作用,富钴区(y<0.5),Co^2^+Co^Ⅲ离子的存在及其浓度是影响NO选择性的主要因素.y=0.5时样品的结构决定了样品的强铁磁性质,并由于Mn^3^+-O^2^--Co^3^+之间不易氧化还原因而对生成NO不利     

二茂金属共轭大环配体配合物的结构及性质

报道了配体Ｎ－（二茂铁基甲基）－１,４,７－氮杂－９－冠－３（Ｌ１）和Ｎ－（二茂钌基甲基）－１,４,７－氮杂－９－冠－３（Ｌ２）的Ｃｏ（Ⅲ）和Ｆｅ（Ⅲ）配合物１－４的合成及电化学性质,配合物「Ｃｏ（Ⅲ）（Ｌ１）２（ＡｃＯ）２（ＯＨ）」（ＣｌＯ４）（Ｉ）２（１）的晶体结构显示这些配合物具有线型排列的四金属中心结构,电化学研究表明：在这些配合物中,客体金属离子通过分子片断的电子传递作用使二茂金属的金属     

On the complex formation equilibria between iron (III) and sulfate ions

The equilibria have been investigated at 25 degrees C in 3 M NaClO4 using potentiometry, glass and redox Fe3+/Fe2+ half-cells, and UV optical absorptiometry. The concentration of the reagents was chosen in the intervals: 10(-4) < or = [Fe(III)] < or = 5.10(-3) M, 0.01 < or = [SO4(2-)]tot < or = 0.65 M. The value of [H+] was kept at 0.1 M or more to reduce the hydrolysis of the Fe3+ ion to less than 1%. Auxiliary constants, corresponding to the formation of Fe(II)-sulfate complexes and to the association of H+ with SO4(2-) ions, were taken from previous determinations. The experimental data could be explained with the equilibria [formula: see text] Equilibrium constants at infinite dilution, log beta 101 degrees = 3.82 +/- 0.17, log beta 102 degrees = 5.75 +/- 0.17 and log beta 111 degrees = 3.68 +/- 0.35, have been evaluated by applying the specific interaction theory.     

ESR-spectroscopy in ionic liquids: Dynamic linebroadening effects caused by electron-self exchange reactions within the methylviologene redox couple

Well-resolved ESR-spectra of the methylviologene radical cation (MV*+) are recorded in room-temperature liquid ions as solvents. The temperature dependences of the ESR-coupling constants are similar to those measured in classical organic solvents. Electron-self exchange rates are reported for the methylviologene redox couple (MV++/MV*+) in 1-butyl-3-methylimidazolium hexafluorophosphate (bmim+ PF6-), 1-butlyl-3-methylimidazolium fluoroborate (bmim+ BF4-) and 1-ethyl-3-imidazolium ethylsulfate (emim+ O3SOEt-) within a temperature range of 350 K < or = T < or = 460 K. The diffusion controlled rate constants observed vary between 8.2 x 10(7) M(-1) s(-1) and 1.2 x 10(9) M(-1) s(-1). From temperature-dependent measurements the activation energies obtained range from 27.4 kJ/mol in emim+ O3SOEt- to 42.1 kJ/mol in bmim+ PF6-, respectively.     

Redox-adaptable copper hosts. Pyridazine-linked cryptands accommodate copper in a range of redox States

A series of structurally characterized copper complexes of two pyridazine-spaced cryptands in redox states + (I,I), (II,I), (II), (II,II) are reported. The hexaimine cryptand L(I) [formed by the 2 + 3 condensation of 3,6-diformylpyridazine with tris(2-aminoethyl)amine (tren)] is able to accommodate two non-stereochemically demanding copper(I) ions, resulting in [Cu(I)(2)L(I)](BF(4))(2) 1, or one stereochemically demanding copper(II) ion, resulting in [Cu(II)L(I)()](BF(4))(2) 3. Complex 3 crystallizes in two forms, 3a and 3b, with differing copper(II) ion coordination geometries. Addition of copper(I) to the monometallic complex 3 results in the mixed-valence complex [Cu(I)Cu(II)L(I)](X)(3) (X = PF(6)(-), 2a; X = BF(4)(-), 2b) which is well stabilized within this cryptand as indicated by electrochemical studies (K(com) = 2.1 x 10(11)). The structurally characterized, octaamine cryptand L(A), prepared by sodium borohydride reduction of L(I), is more flexible than L(I) and can accommodate two stereochemically demanding copper(II) ions, generating the dicopper(II) cryptate [Cu(II)(2)L(A)](BF(4))(4) 4. Electrochemical studies indicate that L(A) stabilizes the copper(II) oxidation state more effectively than L(I); no copper redox state lower than II,II has been isolated in the solid state using this ligand.     

Aggregate manganese Schiff base moieties by terephthalate or acetate: dinuclear manganese and trinuclear mixed metal Mn2/Na complexes

A reaction system consisting of terephthalic acid, NaOH, inorganic Mn(II) or Mn(III) salt, and salicylidene alkylimine resulted in dinuclear manganese complexes (salpn)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (1, salpn = N,N'-1,3-propylene-bis(salicylideneiminato); phth = terephthalate dianion), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (2, salen = N,N'-ethylene-bis(salicylideneiminato)), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(H(2)O) (3), and (salen)(2)Mn(2)(mu-phth) (4), while the absence of NaOH in the reaction led to a mononuclear Mn complex (salph)Mn(CH(3)OH)(NO(3)) (5, salph = N,N'-1,2-phenylene-bis(salicylideneiminato)). In addition, a trinuclear mixed metal complex H[Mn(2)Na(salpn)(2)(mu-OAc)(2)(H(2)O)(2)](OAc)(2) (6) was obtained from the reaction system by using maleic acid instead of terephthalic acid. Five-coordinate Mn ions were found in 4 giving rise to an intermolecular interaction and constructing a one-dimensional linear structure. Antiferromagnetic exchange interactions were observed for 1-3, and a total ferromagnetic exchange of 4 was considered to stem from intermolecular magnetic coupling. (1)H NMR signals of phenolate ring and alkylene (or phenylene) backbone of the diamine are similar to those reported in the literature, and the phth protons are at -2.3 to -10.1 ppm. Studies on structure, bond valence sum analysis, and magnetic properties indicate the oxidation states of the Mn ions in 6 to be +3, which are also indicated by ESR spectra in dual mode. Ferromagnetic exchange interaction between the Mn(III) sites was observed with J = 1.74 cm(-1). A quasireversible redox pair at -0.29V/-0.12V has been assigned to the redox of Mn(2)(III)/Mn(III)Mn(II), implying the intactness of the complex backbone in solution.     

Metal-metal electronic coupling in syn and anti stereoisomers of mixed-valent (FeCp)2-, (RhL2)2-, and (FeCp)(RhL2)-as-indacenediide ions

The extent of metal-metal electronic coupling was quantified for a series of syn and anti stereoisomers of (FeCp)(2)-, (RhL(2))(2)- and (FeCp)(RhL(2))- (L(2)=1,5-cyclooctadiene (cod), L=CO) as-indacenediide mixed-valent ions by spectroelectrochemical and DFT studies. The effect of the syn/anti orientation of the metal units with respect to the planar aromatic ligand indicates that electron transfer occurs through the bridge rather than through space. The nature of the metal was found to be crucial: while homobimetallic diiron species are localised valence-trapped ions (Class II), the dirhodium analogues are almost delocalised mixed-valent ions (borderline and Class III). Finally, despite their redox asymmetry, even in the heterobimetallic iron-rhodium as-indacenediide complexes, strong metal-metal coupling is present. In fact, oxidation of the iron centre is accompanied by electron transfer from rhodium to iron and formation of a reactive 17-electron rhodium site. syn and anti Fe-Rh as-indacenediide complexes are rare examples of heterobimetallic systems which can be classified as borderline Class II/Class III species.     

Electrospray ionization tandem mass spectrometric study of salt cluster ions: part 2--salts of polyatomic acid groups and of multivalent metals

Salt cluster ions formed from 0.05 M solutions of CaCl(2), CuCl(2) and Na(A)B (where A = 1 or 2 and B = CO(3)(2-), HCO(3)(-), H(2)PO(4)(-) and HPO(4)(2-)) were studied by electrospray ionization tandem mass spectrometry. The effects on salt cluster ions of droplet pH and of redox reactions induced by electrospray provide information on the electrospray process. CaCl(2) solution yielded salt cluster ions of the form (CaCl(2))(n)(CaCl)(x)(x+) and (CaCl(2))(n)(Cl)(y)(y-), where x, y = 1-3, in positive- and negative-ion modes, respectively. Upon collision induced dissociation (CID), singly charged CaCl(2) cluster ions fragmented, doubly charged cluster ions generated either singly or both singly and doubly charged fragment ions, depending on the cluster mass, and triply charged clusters fragmented predominantly by the loss of charged species. CuCl(2) solution yielded nine series of cluster ions of the form (CuCl(2))(n)(CuCl)(m) plus Cu(+), CuCl(+), or Cl(-). CuCl, the reductive product of CuCl(2), was observed as a neutral component of positively and negatively charged cluster ions. Free electrons were formed in a visible discharge that bridged the gap between the electrospray capillary and the sampling cone brought about the reduction of Cu(2+) to Cu(+). Upon CID, these cluster ions fragmented to lose CuCl(2), CuCl, Cl, and Cl(2). Na(2)CO(3) and NaHCO(3) solutions yielded cluster ions of the form (Na(2)CO(3))(n) plus Na(+) or NaCO(3)(-). Small numbers of NaHCO(3) molecules were found in some cluster ions obtained with the NaHCO(3) solution. For both Na(2)HPO(4) and NaH(2)PO(4) solutions, ions of the form (Na(2)HPO(4))(h), (NaH(2)PO(4))(i), (Na(3)PO(4))(j), (NaPO(3))(k) plus Na(+), PO(3)(-) or H(2)PO(4)(-) were observed. In addition, ions having one or two phosphoric acid (H(3)PO(4)) molecules were observed from the NaH(2)PO(4) solution while ions containing one sodium hydroxide (NaOH) molecule were observed from the Na(2)HPO(4) solution. The cluster ions observed from these four salts of polyatomic acid groups indicate that changes in pH occur in both directions during the electrospray process principally by solvent evaporation; the pH value of the acidic solution became lower and that of the basic solution higher.     

Kinetic study of the hexacyanoferrate (III) oxidation of dihydroxyfumaric acid in acid media

The kinetics of the hexacyanoferrate (III) oxidation of dihydroxyfumaric acid to hexacyanoferrate (II) and diketosuccinic acid was looked into within the 0.04 to 5.3 M HCl acidity range under different temperatures, ionic strengths, and solvent permittivity conditions. The kinetic effect of alkali metal ions, transition metal impurities, and substrate concentrations have also been analyzed. The observed inhibition effect brought about by addition of the reaction product, hexacyanoferrate (II), is a sign of a complex mechanism. The rate constants remained essentially unchanged up to 1 M HCl, diminished between 1.0 and 3.0 M HCl, and rose above 3.0 M HCl. Depending on the medium acidity, three mechanisms can be put forward, which involve different kinetically active forms. At low acidity, the rate-determining step involves a radical cation and both the neutral and the anion substrate forms are equally reactive ( k 1 = k 2 = 2.18 +/- 0.05 M (-1) s (-1), k -1 = 0.2 +/- 0.03). When the medium acidity is boosted, the rate-determining step involves the neutral dihydroxyfumaric acid and two hexacyanoferrate (III) forms. In the intermediate region the rate constant diminished with rising [H (+)] ( k' 1 = 0.141 +/- 0.01 and k' 2 = 6.80 +/- 0.05). Specific catalytic effect by binding of alkali metal ions to oxidant has not been observed. In all instances it was assessed that the substrate decomposition is slow compared to the redox reaction.     

Cluster ions of diquat and paraquat in electrospray ionization mass spectra and their collision-induced dissociation spectra

Cluster ions such as [Cat+X+nM](+) (n = 0-4); [Cat-H+nM](+) (n = 1-3); and [2(Cat-H)+X+nM](+) (n = 0-2), where Cat, X, and M are the dication, anion, and neutral salt (CatX(2)), respectively, are observed in electrospray ionization (ESI) mass spectrometry of relatively concentrated solutions of diquat and paraquat. Collision-induced dissociation (CID) reactions of the clusters were observed by tandem mass spectrometry (MS/MS), including deprotonation to form [Cat-H](+), one-electron reduction of the dication to form Cat(+.), demethylation of the paraquat cation to form [Cat-CH(3)](+), and loss of neutral salt to produce smaller clusters. The difference in acidity and reduction power between diquat and paraquat, evaluated by thermodynamical estimates, can rationalize the different fractional yields of even-electron ([Cat-H](+) and its clusters) and odd-electron (mostly Cat(+)) ions in ESI mass spectra of these pesticides. The [Cat+n. Solv](2+) doubly charged cluster ions, where n 相似文献