Extraction-polarographic determination of cobalt(II) and nickel(II) as 2,2′-bipyridine complexes in acetonitrile

The tris(2,2′-bipyridine)cobalt(II) complex gives a reversible d.c. wave with E$\text{1}\text{2}$ = ?1.02 V vs. SCE and a sharp differential pulse peak at E_p = ?1.03 V in a salted-out acetonitrile phase. A simple selective method is described for the determination of cobalt(II); down to 0.25 μg of cobalt(II) can be determined in presence of large amounts of Ni, Zn, Cd, Pb, and Cu; iron(III) can be masked with sodium fluoride. The method is applicable to the determination of >0.0l% cobalt in nickel salts and >5 × 10^?5% cobalt in iron salts. Nickel(II) can also be extracted from aqueous solution and determined by differential pulse polarography, even in presence of a 20-fold amount of cobalt(II) by masking with EDTA; >0.01% of nickel in cobalt salts can be determined reproducibly.     

Electrochemical oxidation of α-hyponitrate ion and its analytical applications

α-Hyponitrate ion is electrochemically oxidized at mercury electrodes: the reaction proceeds by an initial 1-electron oxidation to give an anion radical which decomposes to give nitrogen oxide and nitrite as the ultimate products. The d.c. polarographic wave of α-hyponitrate (E_{$\text{1}\text{2}$} = -0.325 V vs. SCE) in 0.1 M sodium hydroxide can be used for the determination of α-hyponitrate in the range 0.08–1.3 mM; a.c. polarography (E_p = -0.30 V vs. SCE) is useful in the range 0.075–1.0 mM. Amperometric titration with 0.05 M hexacyanoferrate(III) is suitable for determinations of 5–20 mg of sodium α-hyponitrate. A.c. polarography at pH 11.0 allows α-hyponitrate to be determined in the presence of 50-fold amounts of hydroxylamine.     

Removal of interference in the differential pulse polarographic determination of progestogens in some combined low-dosage oral contraceptives

Previously published differential pulse methods for the determination of certain progestogens (laevonorgestrel and norethisterone) are not applicable to combined low-dosage oral contraceptives because interference from excipients in the tablets completely eliminates the polarographic response. An ultrafiltration device allows rapid prior extraction of the interfering substances before the polarographic determination in 50% ($\text{v}\text{v}$) methanol—phosphate buffer (pH 6.0). Recoveries of 100 ± 1% were obtained by the recommended method, and data for a range of formulations are in excellent agreement with expected values. Electrode characteristics of the progestogens and interfering substances are reported, based on studies employing cyclic voltammetry at a hanging mercury drop electrode, a.c. polarography and normal pulse polarography. Competitive adsorption processes seem to occur when the progestogen and excipients are simultaneously present.     

High frequency titrations: The mercury(ii)-thiocyanate reaction

Soluble complex-formation of mercury(II) thiocyanate has been studied oscillometrically. The titration of mercury(II) nitrate with thiocyanate gives one inflection corresponding to the formation of Hg(SCN)₂, while in the reverse titration the formation of Hg(SCN)⁺ is also indecated. The method is useful for a rapid determination of very small quantities of mercury or thiocyanate in highly dilute solutions. The titrations can be effected in presence of nitric acid provided its total acidity in the system does not exceed about $\text{1}\text{300}$N. Further Work on the mercury(II) -halide and mercury(II)-cyanide reactions is in progress.     

Regioselective deuteration of aromatic and α,β-unsaturated carboxylic acids via rhodium(III) chloride catalysed exchange with deuterium oxide

$\text{Ortho}$-deuterated aromatic carboxylic acids and β-deuterated α,β-unsaturated caroboxylic acids may be prepared with high regioselectivity by exchange deuteration of the unlabelled acids in the presence of rhodium(III) chloride.     

Determination of stability constants by semi-integral analysis of voltammograms obtained with a computerized electrochemical system

A versatile computerized electrochemical system is used for the determination of stability constants of lead(II) propanoate and 2-hydroxypropanoate complexes by semi-integral linear sweep voltammetry. Semi-integral voltammograms are analogous in characteristics to d.c. polarograms, and the half-wave potentials (E_{$\text{1}\text{2}$}) and limiting currents (i₁) for a depolarizer can be obtained by nonlinear least-squares fitting of semi-integrally transformed voltammograms. An advantage of the proposed method is that E_{$\text{1}\text{2}$} and i₁ values are obtained from a single mercury drop (hanging or dropping mercury electrode); working time is reduced while accuracy and precision are maintained. The computer-controlled system provides automated reagent addition, signal generation, response measurement and sampling, data evaluation, etc. The results agree well with those obtained by the usual d.c. polarographie method.     

Electrochemical studies of homocysteine and homocystine at mercury electrodes

The behaviour of homocysteine and cysteine at mercury electrodes is compared. The one-electron oxidation associated with thiols is shown to be the same for both compounds in acidic phosphate buffer, giving rise to an adsorbed thiol—mercury complex, (RS)₂Hg, at the electrode surface. Formation of this complex is utilized in the cathodic stripping voltammetric determination of homocysteine; the detection limit is 10^?9 M after a deposition time of 90 s at a hanging mercury drop electrode. The similar E_{$\text{1}\text{2}$} values for homocysteine and cysteine mean that prior separation is needed for their individual determination. Amperometric detection with a mercury-coated goal electrode after separation by cation-exchange liquid chromatography provides a method for the simultaneous determination of both compounds. Reduction of homocystine at the mercury electrode is also compared to that of cystine. The more negative reduction potential, and the maximum observed for homocystine on d.c. polarograms, which is not seen for cystine, is attributable to different reaction kinetics at the mercury electrode; the products of both the 2-electron reductions are the corresponding thiol-containing amino acids.     

Direct current and differential pulse polarographic behaviour of benzylpenicilloic acid

The differential pulse and direct current polarographic behaviour of benzylpenicilloic acid (BPA) is discussed. In pH 9.2 borate buffer, the single anodic wave (E_{$\text{1}\text{2}$} = -0.25 V) obtained is diffusion-controlled at concentrations less than 2 × 10^-5 M but adsorptioncontrolled in 10^-4 M solution. Cyclic voltammetry at a hanging mercury drop electrode shows that the electrode reaction is reversible at pH 9.2. The differential pulse peak current is linearly related to concentration in the range 10^-6—2 × 10^-5 M. Penicillamine yields an anodic peak well separated from the BPA peak. Both substances may be determined in each other's presence. Intact penicillin decreases the BPA peak but the linearity between i_p and BPA concentration is maintained.     

Polarographic determination of iron(II) and iron(III) complexes with edta

The iron(II) and iron(III) complexes with EDTA can be determined separately and in mixtures in acetate-buffered medium at pH 4.0. The E_{$\text{1}\text{2}$}values are in the range ?0.105 to ?0.112 V vs. SCE. Linear calibration plots are obtained over the range 0–1.0 mM for each oxidation state. A sample-handling procedure for avoiding oxidation of iron(II) species is described. It is shown that the acetate buffer system does not affect the stability of the iron-EDTA complexes.     

Contributions to the complexometric determination of cation mixtures: Simultaneous titration of iron(iii) and aluminium in the presence of ammonium thiocyanate as indicator

With thiocyanate as indicator iron(III) and aluminium(III) can be titrated simultaneously if [Fe⁺³]/[Al⁺³] ? $\text{1}\text{4}$; iron(III) is titrated directly with EDTA, and aluminium(III) is determined by back-titration of the excess of EDTA with cobalt nitrate solution in an acetone-water medium.     

Polarography of disodium pentacyanonitrosylferrate(II): Part 2. Determination at Therapeutic Levels in Serum,Plasma, and Whole Blood

Disodium pentacyanonitrosylferrat(II) (sodium nitroprusside) is determined at therapeutic (ng ml^?1) levels in plasma, serum and blood with conventional and high-performance differential pulse polarography (d.p.p. and h.p.d.p.p.) at a dropping mercury electrode or a static mercury drop electrode. Serum or plasma (3 ml) is treated with perchloric acid containing 1 mg ml^?1 potassium hexacyanoferrate(II), centrifuged for 10 min and subjected to polarography. For spiked serum, calibration graphs are linear over the range 30–1000 ng ml^?1 sodium nitroprusside, regardless of the polarographic technique; the estimated detection limit is 15 ng ml^?1 (5 × 10^?8 M). Calculated therapeutic levels range from 100 to 1000 ng ml^?1. Similar results were obtained for spiked plasma. A similar procedure is suitable for whole blood and was used to study the in-vitro degradation of sodium nitroprusside (200 ng ml^?1) on incubation at 37°C. The in-vitro loss is rapid (t_{$\text{1}\text{2}$} ≈ 6 min) but meaningful in-vivo levels can be obtained when the blood is collected in a 0.9% sodium chloride solution at 0°C. Thiocyanate, the main metabolite of nitroprusside, and thiosulphate, which is a potential antidote for cyanide, do not interfere.     

Polarographic reduction of pertechnetate

Oxidation states were identified for the products of electrolytic reduction of pertechnetate at the mercury cathode in a variety of media, and for the products of reoxidation upon reversing the cell current. Tast polarography, pulse polarography and triangular-wave voltammetry were employed. The first cathodic wave in acidic phosphate was identified as Tc(VII) → Tc(III) by means of the ratio between it and the Tc(III) → Tc(IV) reoxidation wave obtained on anodic-sweep pulse polarography. This wave was then used as a standard to determine values of n in other media of the same ionic strength. The first wave in acidic media occurred at pH-dependent potential and was found generally to correspond to the formation of Tc(III). The Tc(III) could in some media be reoxidized at the electrode to Tc(IV) or Tc(V). For the second wave in acidic media, which occurred at ?0.9 V, diffusion current measurements indicated that n≤7 with a catalytic component preventing determination of the exact value. In alkaline or unbuffered media the first wave occurred at ?0.8 V and a second wave was sometimes seen at ?1.0 V. The wave heights in alkaline media, while generally proportional to concentration of pertechnetate and varying with drop time in the manner expected for a diffusion current, often corresponded to non-integral values of n. In certain basic media the reduction of pertechnetate led to the formation of an insoluble oxidizable surface film. Under all conditions investigated the reduction of pertechnetate proved to be irreversible.     

Sterically crowded cyclopropanation catalysts. Syn-selectivity using rhodium(III)porphyrins

Rhodium(III)porphyrins catalyze the decomposition of ethyl diazoacetate and the transfer of ethoxy-carbonylcarbene to alkenes to form cyclopropanes in moderate to high yields. When compared with other catalysts a large syn-selectivity was observed on reaction with cis-alkenes. This selectivity increased with the size of the substituents, and suggested a preferential direction of approach of the alkene towards a rhodium—carbene complex.     

Electrochemistry of lanthanides in molten chloroaluminates: Part I. The electrochemical behaviour of Eu(III), Yb(III) and Sm(III)

The electrochemical behaviour of Eu(III), Yb(III,II) and Sm(III,II) has been investigated in NaCl-AlCl₃ mixtures, in a temperature range between 150 and 250°C. Principal investigation methods are cyclic voltammetry, pulse polarography and chronoamperometry. The three tervalent lanthanides can be reduced reversibly and solutions of divalent oxidation states are stable. E_1/2 potentials measured with respect to an Al electrode in a saturated melt are located respectively at 2.295 V (Eu), 1.630 V (Yb) and 1.080 V (Sm). In acidic chloroaluminates, the three investigated lanthanides are more oxidizing than in other more complexing solvents. If the acidity of the melt is decreased, precipitation of the trichloride (or the dichloride) occurs and the solubility product of the different species is directly related to the cationic size.     

Oxidative addition of dimethylphosphite to iridium(I) and rhodium(I) complexes: Stereoselective reduction of 4-t-butylcyclohexanone

Dimethylphosphite, (CH₃O)₂P(O)H, adds oxidatively to iridium(I) and rhodium(I) complexes to give hydrido-iridium(III) or -rhodium(III) dimethylphosphonate complexes. A complex Ir(H)Cl[P(O)(OCH₃)₂][P(OH)(OCH₃)₂]₃ obtained from [IrCl(C₈H₁₄)₂]₂ and dimethylphosphite catalyses the stereo-selective reduction of 4-t-butylcyclohexanone to $\text{97}\text{3}$cis/trans-4-t-butylcyclohexanol, the ratio being identical with that obtained using the Henbest catalyst iridium(IV) chloride, phosphorous acid or one of its esters, and aqueous isopropanol.     

Polymeric optical sensors for selective and sensitive nitrite detection using cobalt(III) corrole and rhodium(III) porphyrin as ionophores

Cobalt(III) 5,10,15-tris(4-tert-butylphenyl) corrole with a triphenylphosphine axial ligand and rhodium(III) 5,10,15,20-tetra(p-tert-butylphenyl) porphyrin are incorporated into plasticized poly(vinyl chloride) films to fabricate nitrite-selective bulk optodes via absorbance measurements. The resulting films yield sensitive, fast and fully reversible response toward nitrite with significantly enhanced nitrite selectivity over other anions including lipophilic anions such as thiocyanate and perchlorate. The selectivity patterns differ greatly from the Hofmeister series based on anion lipophilicity and are consistent with selectivity obtained with potentiometric sensors based on the same ionophores. The optical nitrite sensors are shown to be useful for detecting rates of emission of nitric oxide (NO) from NO releasing polymers containing S-nitroso-N-acetyl-DL-penicillamine.     

Investigations into the catalytic activity of rhodium(III) in red-ox reactions by capillary zone electrophoresis

Speciation of rhodium(III) in different acidic media has been studied by capillary zone electrophoresis (CZE). Depending on the nature of the acid, rhodium was shown to occur in the form of positive, neutral and/or negatively charged complexes. The relationship between the distribution of rhodium forms and its catalytic action on the oxidation of N-methyldiphenylamine-4-sulfonic acid by periodate ions has been investigated. It was found that only positively charged complexes of rhodium, such as those dominating in perchloric acid solutions, catalyzed a given reaction to form a colored oxidation product. The rate of the catalyzed reaction was optimized with respect to the pH, reagent and oxidant concentration levels, ionic strength, concentration of the catalyst, as well as the presence of interfering ions. The developed kinetic spectrophotometric method features rather high sensitivity (limit of determination 10 μg l⁻¹) and tolerance for most platinum metals and was applied to a complex industrial sample of a platinum concentrate.     

Polarographic determination of the stability constants of metal complexes based on the shifts in half-wave or peak potentials of the anodic oxidation of mercury: methylthioacetato- and 2,2′-thiobisacetato complexes

The stability constants of metal-ion complexes, other than those of mercury ions, can be determined from the shifts, caused by an excess of that metal ion, in the anodic waves of mercury oxidation in the presence of the ligand.Let a solution contain L, a ligand that can react with mercury ion from the anodic oxidation of mercury to form the complexes HgL_p. The half-wave potential of the anodic wave will be shifted by the presence of an excess of a metal ion M, which can also react with L forming the complexes M_jL (where j = 1, $\text{1}\text{2}$,…1/N). A general expression is derived relating the half-wave potential shift ΔE_{$\text{1}\text{2}$} to the overall stability constants. If the excess of metal ion M is great enough for the 1:1 complex to predominate in solution (and if HgL₂ is the predominating mercury complex), for reversible, diffusion-controlled processes the general equation can be simplified to:

where c_M is the total concentration of metal ion M.This equation provides an easy and fast method for β₁ determination. The simplified equation is best suited for experimental data obtained from techniques such as DP, AC₁ and AC₂ polarography, whose increased precision in ΔE measurement enables poorly-developed dc-polarographic anodic waves to be used for β₁ determination. Since the metal-to-ligand concentration ratio must be large in order to apply the simplified equation, the determination can be carried out at very small ligand concentrations. This fact renders the new method especially useful when the ligand solubility does not allow the high ligand concentrations needed in the DeFord—Hume method to be reached. The adequacy of the deduced equations when applied to polarographic processes which are irreversible or not controlled by diffusion is discussed.The simplified equation is tested using several metal complexes of methylthioacetate and 2,2′-thiobisacetate ligands and comparing some of the values obtained from experimentally measured ΔE's with known β₁ values taken from the literature. Good agreement is found. For the U(VI)—methylthioacetate complex, which has not been previously reported in the literature, log β₁ = 1.75 ± 0.1.     

Thermal properties of rhodium(III) chloride

Thermal decomposition of rhodium(III) chloride under inert, oxidative and reductive gas atmospheres was investigated in order to determine its thermal properties. Stoichiometries of the reactions occurring during heating are described. it is suggested that the chemical formula of soluble rhodium(III) chloride should be presented as RhCl₃·HCL·xH₂O. Cold crystallisation of anhydrous rhodium(III) chloride at a temperature of about 500°C was established. The procedure for quantitative determination of volatile matter (water and hydrochloric acid) content and rhodium content by thermogravimetry is given and discussed. The repeatability and reproducibility of the method are estimated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Palladium-catalyzed asymmetric cyclization of methyl (E)-oxo-9-phenoxy-7-nonenoate and its analogs

Asymmetric cyclizations of methyl (E)-3-oxo-9-phenoxy-7-nonenoate ($\text{1}$) or methyl (E)-3-oxo-9-(methoxycarbonyl)oxy-7-nonenoate ($\text{4}$) without added base were carried out in the presence of a catalytic amount of palladium(II) acetate and chiral diphosphine as ligands. Allylic carbonate $\text{4}$ reacted by use of Pd(OAC)₂-(S)-(R)-BPPFA at room temperature to give (R)-3-vinylcyclohexanone ($\text{3}$), after decarboxylation, in up to 48% e. e.