Mixed-ligand complexes of gold(I) and silver(I) with heterocyclic thiones

Summary Novel mixed-ligand complexes of Ag¹ and Au¹ containing triphenylphosphine (TPP) and heterocyclic thiones, of general formula [TPP–M–L]Cl and [(TPP)₂–M–L]Cl, where L=imidazolidine-2-thione (Imt), 1,3-diazinine-2-thione (Diaz) or N-isopropylimidazolidine-2-thione (iPrImt) have been prepared. The spectroscopic data are consistent with S-donation in all complexes. The magnitude of high-field shift in carbon-13 n.m.r. of the thioureide carbon on complexation is interpreted in terms of coordination geometry around the metal atoms. The mixed-ligand complexes are structurally similar to some of the commonly used antiarthritic Au¹ drugs and are thus potentially useful in chemotherapy.     

Interaction of Silver(II) and Gold(III) meso-Tetraphenylporphine Complexes with Concentrated Sulfuric Acid

The reaction of meso-tetraphenylporphine (H₂TPP) with Ag(OAc) or KAuCl₄in boiling acetic acid affords Ag^IITPP and (Cl)Au^IIITPP complexes. The complexes are purified by column chromatography and identified by thin layer chromatography and IR and electronic absorption spectroscopy. The transfer of a proton to the porphyrin macrocycle and dissociation of the complexes via the metal–nitrogen bonds in concentrated H₂SO₄at different temperatures and H₂SO₄concentrations are studied by spectrophotometric and kinetic methods. The formation of the stable ion-molecular H-associate of the metalloporphyrin with a doubly-charged metal cation is found for the first time for silver(II) tetraphenylporphine. Gold(III) tetraphenylporphine exists in a sulfuric acid solution in the monomolecular form. The numeric values of true rates and activation parameters of the complex dissociation are determined. The stability, state in solution, and mechanism of dissociation of the silver(II) and gold(III) tetraphenylporphine complexes are determined by the metal electronic configuration of the complex cation and, especially, by the contribution of the component to the donor–acceptor M–N interaction.     

Kinetics of ammoniation of some halobis(ethylenediamine)-rhodium(III) perchlorates in liquid ammonia

Summary The ammoniation ofcis-[Rh(en)₂Cl₂] · (ClO₄) in liquid NH₃ was studied at constant ionic medium of 0.20 m perchlorate in the 0 to 35° range. The complex reacts in two distinct steps to givecis-[Rh(en)₂(NH₃)₂] · (ClO₄)₃, with the intermediate formation ofcis-[Rh(en)₂(NH₃)Cl] · (ClO₄)₂. Both steps follow a conjugate-base mechanism. Activation parameters were obtained for the acid-base preequilibrium and the rate-determining step. The entropies of activation for the rate-determining step are 0 and –42 JK^–1mol^–1 for the first and second ammoniations respectively. These values are considerably lower than those found for the cobalt(III) analogues. The entropy changes for the acid-base equilibria are –84 and –36 JK^–1mol^–1 respectively, which is less negative than those values found for the cobalt(III) analogues. Trans-[Rh(en)₂I₂] · (ClO₄) ammoniates totrans-[Rh(en)₂(NH₃)I] · (ClO₄)₂. The contribution of spontaneous ammoniation to the overall reaction oftrans-[Rh(en)₂I₂] · (ClO₄) is negligible, so the uniqueness oftrans-[Co(en)₂Cl₂] · (ClO₄) among cobalt(III) complexes in this respect is not reproduced for thetrans-dihalotetraamine structure in rhodium(III) complexes. A comparison of cobalt(III) and rhodium(III) amines with respect to activation parameters and the influence of formal charge of the metal complex on reactivity indicates a more associative type of activation for rhodium(III).     

Adsorption properties of charcoal impregnated with stannic chloride

Adsorption behaviour of the individual tracer ions:¹³⁴Cs(I),^85,89Sr(II),^131,133Ba (II),⁹⁰Y(III),¹⁴¹Ce(III),^152,154Eu(III),⁹⁵Zr(IV),^175,181Hf(IV),⁹⁵Nb(V),⁶⁰Co(II),¹¹⁵Cd(II),^99mTc(VII), and¹³¹I(-I) on charcoal impregnated with stannic chloride from Hcl solutions, was investigated. Batch equilibrium distribution coefficients of the respective ions indicated strong anion exchange properties towards impregnated charcoal. The column breakthrough sorption capacity was of the order of 0.62–0.66 meq·g^–1 of dry adsorbent. Small chromatographic columns of impregnated charcoal could achieve rapid and quantitative separation procedures in HCl medium. Strongly adsorbed anions such as TcO ₄ ^– and I^– ions could be eluted with NH₄SCN and NH₄NO₂ eluents, respectively.     

Kinetics and Mechanism of Electroreduction of Ammonia Complexes of Cobalt(II) on a Dropping Mercury Electrode

Effects of concentrations of ammonia (0.3–5.8 M) and supporting electrolytes (NaF, NaClO₄; 0.1–0.5 M) on the kinetics of electroreduction of ammonia complexes of cobalt(II) at a dropping mercury electrode are studied. Most experiments are performed with low concentrations of cobalt(II) complexes (1 × 10^–5 to 2 × 10^–5 M) in the absence of a polarographic maximum. The dependence of the half-wave potential of the reversible cathodic wave pertaining to the reduction of ammonia complexes of cobalt(II) on the concentration of ammonia molecules is obtained. It is found from the dependence that, at ammonia concentrations of 0.5–2.6 M, the slow electrochemical stage involves predominantly complexes Co(NH₃)₂ ²⁺. At higher ammonia concentrations, the stage involves complexes Co(NH₃) _k ²⁺ (k > 2), which form in preceding chemical stages from complexes Co(NH₃) _i ²⁺ (i = 3–6) that are predominant in solution. Values of the diffusion coefficients for complexes Co(NH₃) _i ²⁺, apparent transfer coefficients, and rate constant of the process of electroreduction of ammonia complexes of cobalt(II) are determined. The reasons for the complicating effect the insoluble products of reduction of cobalt(II) complexes have on the shape of polarographic waves are discussed.     

Use of Different Salt Solutions in Salting-Out TLC of Co(III) Complexes on Silica Gel

Saturated aqueous solutions of 28 different salts have been studied as a potential mobile phases for salting-out thin-layer chromatography, on silica gel, of a series of four mixed bis-aminocarboxylato cobalt(III) complexes. In addition, by linear regression analysis of chromatographic data obtained for fifteen mixed aminocarboxylato Co(III) complexes (four series) with solutions of ammonium chloride, three alkali metal chlorides, and four alkaline earth metal chlorides, four linear dependences previously established on different adsorbents with (NH₄)₂SO₄ solutions were confirmed. The qualities of the separations achieved with the salts were compared and Li⁺, Mg²⁺, and Ca²⁺ chlorides are proposed as the most suitable.     

High-Performance Liquid Chromatography of Metal Tetra-4-tert-Butylphthalocyanines

The chromatographic behavior of tetra-4-tert-butylphthalocynine; its 1 : 1 complexes of Zn(II), Cu(II), Mg(II), Ni(II), Pd(II), Co(II), Rh(III), and Sn(IV); 1 : 2 complexes of Lu(III), Dy(III), and Tb(III); and a linear dimer of copper hexa-4-tert-butyldiphthalocyanine were studied on hydrophobized, aminated, and unmodified silica gels. The retention of the above complexes was studied as a function on the composition of the mobile phase, the nature of the metal atom, the number of macrocycles in the ligand, and the length of the chromatographic column. It was shown that hydrophobized silica gels with acetone, acetonitrile–acetate (1 : 1), methanol–ethyl acetate (1 : 1), and dimethylformamide mobile phases are the most selective systems for determining the purity of the phthalocyanines. For each compound, an individual, usually symmetrical peak was observed. The parameters of these peaks can be used for the rapid identification and sensitive determination of the compounds studied. The detection limits were at a level of n× 10^–8M.     

Thermodynamic properties of chloro-complexes of silver chloride in aqueous solution

Available data on the solubility of silver chloride in aqueous solutions of HCl, NaCl, KCl, LiCl, and NH₄Cl, along with potentiometric measurements of the activity of Ag⁺ in aqueous NaCl–NaClO₄ mixtures, have been analyzed to obtain the thermodynamic properties of the (AgCl)⁰, AgCl ₂ ^– , AgCl ₃ ^2– , and AgCl ₄ ^3– complexes. Results obtained include the stability constants of the complexes and 25°C, the virial parameters needed to calculate the activity coefficients of the complexes and the heats of the reactions by which they are formed. These results are sued to calculate tables of recommended values for the solubility of silver chloride in the host solutions as a function of concentration from 0 to 150°C and to make a critical evaluation of the reliability of previously published data.     

Cobalt(II) complexes of 1,2-(diimino-4′-antipyrinyl)ethane and 4-N-(4′-antipyrylmethylidene)aminoantipyrine

Cobalt(II) complexes of the Schiff bases 1,2-(diimino-4-antipyrinyl)ethane (GA) and 4-N-(4-antipyrylmethylidene)aminoantipyrine (AA) have been prepared and characterised by elemental analysis, electrical conductance in non-aqueous solvents, i.r. and electronic spectra, as well as by magnetic susceptibility measurements. The complexes have the general formulae [Co(GA)X]X (X = ClO^– ₄ or NO₃ ^–), [Co(GA)X₂] (X = Cl^–, Br^– or I^–), [Co(AA)₂]X₂ (X = ClO₄ ^–, NO₃ ^–, Br^– or I^–) and [Co(AA)Cl₂]. GA acts as a neutral tetradentate ligand, coordinating through both carbonyl oxygens and both azomethine nitrogens. In the perchlorate and nitrate complexes of GA one anion is coordinated in a bidentate fashion, whereas in the halide complexes both anions are coordinated to the metal, generating an octahedral geometry around the Co ion. AA acts as a neutral bidentate ligand, coordinating through the carbonyl oxygen derived from the aldehydic moiety and the azomethine nitrogen. Both anions remain ionic in the perchlorate, nitrate, bromide and iodide complexes of AA, whereas both anions are coordinated to the metal ion in the chloride complex, resulting tetrahedral geometry around the Co ion.     

Synthesis and Characterization of a New (E,E)-Dioxime and its Homonuclear Complexes

N′-(4′-Benzo[15-crown-5]naphthylaminoglyoxime (H₂L) and its sodium chloride complex (H₂L·NaCl) have been prepared from 2-naphthylchloroglyoxime, 4′-aminobenzo[15-crown-5] and sodium bicarbonate or sodium bicarbonate and sodium chloride. Nickel(II), cobalt(II) and copper(II) complexes of H₂L and H₂L·NaCl have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The BF₂⁺-capped Ni(II), Co(III) and mononuclear complexes of thevic-dioxime were prepared. The macrocyclic ligands and their transition metal complexes have been characterized on the basis of IR, ¹H NMR spectroscopy and elemental analyses data.     

Sedimentation potential of complexes of nitroamminecobalt(III) in aqueous solution at 25°C

Sedimentation potentials (SP) were measured for a series of nitroamminecobalt(III) chlorides in aqueous solution. The magnitudes of the sedimentation potentials varied with the number of NO ₂ ^– ligands in the complexes and a definite positive signal was observed for a neutral complex [Co(NO₂)₃(NH₃)₃]⁰. The division of the partial molar volumes of nitroamminecobalt(III) complexes based on the observed SP values resulted in comparable values of the partial molar volume for the Cl^– ion, suggesting no appreciable hydrolysis nor ionic association occur for these nitroammine-cobalt(III) complexes.     

The coordination chemistry of macrocyclic diamides. Transition metal complexes of 5,7-dioxo-1,4,8,11-tetraazacyclotetradecane

Summary A convenient preparation of the 14-membered macrocyclic diamide 5,7-dioxo-1,4,8,11-tetraazacyclotetradecane (LH₂) is described. The pK _NH ⁺ values of the ligand are pK₁ = 5.76 and pK₂ = 9.63 at 25° and I = 0.1 mol dm^–3 (KNO₃). With metal ions able to ionise amide hydrogens, the ligand acts as a planar quadridentate, L^2–. Thus copper(II) and nickel(II) give the neutral complexes ML, and conductivity measurements confirm that they are nonelectrolytes in aqueous solution. Both the nickel(II) and copper(II) complexes are acid labile unlike the analogues of 1,4,8,11-tetraazacyclotetradecane (cyclam).The cobalt(III) complex [CoL(NH₃)₂]Cl has been characterised and¹H n.m.r. measurements established the N-meso stereochemistry at the chiral nitrogen centres.     

Zur Kenntnis der Sulfito-kobalt(III)-Ammine. III. Hydrogensulfitokobalt(III)-Ammine

Sulphito Cobalt(III) Ammines. III. Hydrogensulphito Cobalt(III) Ammines Concentrated acids react with [CoSO₃(NH₃)₅]⁺ salts hydrogen- sulphitopentaamminecobalt(III) complexes. [Co(HSO₃)(NH₃)₅]Cl₂, [Co(HSO₃)(NH₃)₅]Br₂ and [Co(HSO₃)(NH₃)₅](HSO₄)₂·H₂O have been isolated. These substances are yellow coloured in contrast to an earlier work which reported red colour. Furthermore, the hydrogensulphitoacidotetreaammine complexes [Co(HSO₃)Cl(NH₃)₄]Cl, [Co(HSO₃)Cl(NH₃)₄]ClO₄·H₂O, [Co(HSO₃)Br(NH₃)₄]Br and [Co(HSO₃) CN(NH₃)₄]Cl habe been prepared. [Co(HSO₃)Br(NH₃)₄]Br is losing spontaneously HBr forming [CoSO₃Br(NH₃)₄]. The neutral complex [Co(HSO₃)SO₃(NH₃)₄]·1/2H₂O has been obtained from cis- NH₄[Co(SO₃)₂(NH₃)₄] and HCl. The absorption spectra in the IR, visible and UV region are reported and discussed. The HSO₃ group is coordinated to Co through the S atom. The Co? S bond is weaker than in the sulphito complexes as concluded from the RAMAN spectrum. In the new complexes, the hydrogensulphito ligand causes a minor trans effect than the sulphito ligand.     

Coordination Polyhedra OsXn(X = F, Cl, Br, I) in Crystal Structures

The Voronoi–Dirichlet polyhedra (VDP) and the method of intersecting spheres were used to perform crystal-chemical analysis of compounds containing complexes [Os _a X _b ] ^z–(X = F, Cl, Br, I). Atoms of Os(V) at X = F and Cl, of Os(IV) at X = Cl, Br, and of Os(III) at X = Br were found to exhibit a coordination number of 6 with respect to the halogen atoms and to form OsX₆octahedra. The coordination polyhedra of Os(III) for X = Cl, I are square pyramids OsX₄. Each Os(III) atom forms one Os–Os bond; as a consequence, the OsBr₆octahedra share a face in forming Os₂Br^3– ₉complexes, while the OsX₄pyramids (X = Cl, I) dimerize to produce [X₄Os–OsX₄]^2–ions. The influence of the valence state of the Os atoms and of the nature of the halogen atoms on the composition and structure of the complexes formed and some characteristics of the coordination sphere of Os were considered.     

Coated wire chromium(III) ion-selective electrode based on azamacrocycles

Tetraazacyclotetradecane, tetratosyltetraaza 12C4, and tritosyltriaza 9C3 have been explored as electroactive materials for preparing coated wire ion-selective electrodes (CWISEs) for Cr(III) ions. The best performance was observed for the membrane comprising electroactive material (tetratosyltetraaza 12C4), plasticizer (dibutyl phthalate), and poly(vinyl chloride) in the optimum ratio 5:60:35 (w/w). Linear Nernstian response for this electrode was obtained over the total Cr(III) concentration range of 1×10^–1 to 1×10^–7 M in 0.05 M NH₄NO₃ medium, with a slope of 20±1 mV per decade change. The working pH range of the electrode was 1.8–5.5. Selectivity coefficients of some mono, divalent, and trivalent metal ions were determined. Analyses of electroplating bath solutions, chromating, and effluent samples have been carried out using this CWISE and the results are found to be comparable with those obtained by using conventional methods or by AAS.     

Interaction of N-(aryl)picolinamides with iridium. N–H and C–H bond activations

Reaction of N-(4-R-phenyl)picolinamide (R = OCH₃, CH₃, H, Cl and NO₂) with [Ir(PPh₃)₃Cl] in refluxing ethanol in the presence of a base (NEt₃) affords two yellow complexes (1-R and 2-R). The 1-R complexes contain an amide ligand coordinated to the metal center as a monoanionic bidentate N,N donor along with two triphenylphosphines, a chloride and a hydride. The 2-R complexes contain an amide ligand coordinated to the metal center as a monoanionic bidentate N,N donor along with two triphenylphosphines and two hydrides. Similar reaction of N-(naphthyl)picolinamide with [Ir(PPh₃)₃Cl] affords two organometallic complexes, 3 and 4. In complex 3 the amide ligand is coordinated to the metal center, via C–H activation of the naphthyl ring at the 8-position, as a dianionic tridentate N,N,C donor, along with two triphenylphosphines and one chloride. Complex 4 is similar to complex 3, except a hydride is bonded to iridium instead of the chloride. Structures of the 1-OCH₃, 2-Cl and 4 complexes have been determined by X-ray crystallography. All the complexes are diamagnetic, and show characteristic ¹H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows a Ir^III–Ir^IV oxidation within 0.50–1.16 V vs. SCE and a reduction of the coordinated amide ligand within −1.02 to −1.25 V vs. SCE.     

The electronic effect in supramolecular self-assembly of <Emphasis Type="Italic">para-</Emphasis>substituted tetraphenylporphyrinatozinc(II) with imidazolyl-linked porphyrinatomanganese(III) by coordinative bonding

The supramolecular self-assembly of para-substituted tetraphenylporphyrin complexes of zinc(II), Zn(p-X)TPP, with imidazolyl-linked porphyrinatomanganese(III), Mn(p-lmBPTPP)Cl, driven by coordinative bonding has been investigated by fluorescence spectra, electrospray mass spectrometry, ¹H-n.m.r. and u.v.–vis. spectra. The association constants of the supramolecular complexes, K_c, were calculated using fluorescence spectroscopic titration data at suitable dilute concentration ranges in which the fluorescent quenching of Zn(p-X)TPP by Mn(p-ImBPTPP)Cl is a static process. The electronic effect in the supramolecular self-assembly of para-substituted . porphyrinatozinc(II) with imidazolyl-linked porphyrinatomanganese(III) is discussed. The non-linear dependence of log K_c on the Hammett constants was found, which suggested that the electronic effect in para-substituents of tetraphenylporphyrin complexes of zinc(II) is an important, but not a sole factor effecting the association constants of the Zn(p-X)TPP–Mn(p-ImBPTPP)Cl supramolecular complexes. The results indicate that the closed conformation of the Zn(p-X)TPP–Mn(p-ImBPTPP)Cl supramolecular complex is another important factor effecting the association constants of the Zn(p-X)TPP–Mn(p-ImBPTPP)Cl supramolecular complexes.     

Base hydrolysis of mono-alkylsubstituted chloropentaamminecobalt(III) complexes

Summary The preparation of the series ofcis- andtrans-[Co(NH₃)₄(RNH₂)Cl]²⁺ complexes (withcis, R = Me orn-Pr andtrans, R = Me, Et,n-Pr,n-Bu ori-Bu) is described. The u.v-visible spectra indicate a decrease of the ligand field on increasing chain length. Infrared spectra show an enhanced Co-Cl bond strength compared to the pentaammine. Partial molar volumes of the complex cations do not reveal steric compression. From proton exchange studies in D₂O it follows that [Co(NH₃)₅Cl]²⁺ and thecis- andtrans-[Co(NH₃)₄-(CH₃NH₂)C1]²⁺ complexes exchange the amine protons on the grouptrans to the chloro faster than those on thecis. A coordinated methylamine group exchanges its amine protons slower than a corresponding NH₃ group in the parent pentaammine, but the methyl introduction accelerates the exchange of the other NH₃ groups. The aquation of thetrans-alkylamine complexes (studied at 52° C) is acceleratedca. 10 times compared to the parent pentaammine, irrespective of the nature of the alkyl group. Thecis complexes do not show this acceleration of aquation. In base hydrolysis (studied at 25° C) thecis complexes are the most reactive (a factor 20 over the parent ion). Thecis/trans product ratio in base hydrolysis and the competition ratio in the presence of azide ions were calculated from the 500 MHz¹H n.m.r. spectra, which display distinctly different alkyl resonances for each individual complex. Thecis ions react under stereochemical retention of configuration; thetrans compounds give 10±1%trans tocis rearrangement. The ionic strength (4 mol dm^–3) and the pH do not affect this result. The same product ratio is obtained in methanol-water and DMSO-water mixtures. Ammoniation in liquid ammonia gives the same ratios as in base hydrolysis, base-catalyzed solvolysis in neat methylamine gives stereochemical retention for both thecis- andtrans-methylamine ion. The product competition ratio (Co-N₃)/(Co-OH₂) for thecis compounds and the bulkier amines (R =n- andi-Bu), 15–25% at 1 mol dm^–3N ₃ ^– , isca. twice that of thetrans compounds and the pentaammine. The results are interpreted in the classical conjugate base mechanism, and discussed in the context of current ideas about stereochemistry of base hydrolysis.Prof. C. R. Píriz Mac-Coll from Uruguay is a guest at the Free University of Amsterdam.     

Chemische Effekte des isomeren Überganges von Brom-80m in Pentamminkobalt(III)-und Bisäthylendiaminkobalt(III)-bromiden

Zusammenfassung Die chemischen Effekte des isomeren Überganges von^80mBr wurden bei Temperaturen von–78° C und–196° C an mit^80mBr markierten Proben von [Co(NH₃)₅ X]Br_3.2 nH₂O und [Co(en)₂ X _2']Br_3.1 nH₂O untersucht (X=NH₃, NCS, NO₂, OH₂, ONO, ONO₂, F, Cl, Br, I, undX'=en, NH₃, NCS, Cl, Br). Es zeigte sich, daß die Ligandenausbeute an⁸⁰Br, in den Komplexen mit abnehmender Frequenz des Maximums in der ersten Absorptionsbande des [Co(NH₃)₅ X] und des [Co(en)₂ X _2'] zunimmt. Mit anderen Worten, weniger stabile, Liganden werden leichter von Radiobrom ersetzt als Folge des isomeren Überganges in festen Komplexen.

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Chemical effects of the isomeric transition of^80mBr in pentammincobalt(III) and bisethylenediaminecobalt(III) bromides

The chemical effects of the isomeric transition of^80mBr were investigated at temperatures of–78° C and–196° C with^80mBr-labeled samples of [Co(NH₃)₅ X]Br_3.2 nH₂O and [Co(en)₂ X _2']Br_3.1 nH₂O (X=NH₃, NCS, NO₂, OH₂, ONO, ONO₂, F, Cl, Br, I, andX'=en, NH₃, NCS, Cl, Br). The ligand yield of⁸⁰Br in the complexes was found to increase with the decrease in the frequency of the maximum in the first absorption band of [Co(NH₃)₅ X] and [Co(en)₂ X _2']. In other words, less stable ligands were more easily replaced by radiobromine as a consequence of isomeric transition in solid complexes.

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Mit 1 Abbildung

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Herrn Prof. Dr.E. Broda zum 60. Geburtstag gewidmet.     

Determination of cobalt in the presence of high concentrations of zinc by differential pulse polarography

Summary Cobalt(II) can be determined in 0.1 mol/l Na₃citrate + 0.1 mol/l NH₄Cl + 0.08% dimethylglyoxime as supporting electrolyte in the presence of a 50 000-fold excess of zinc by differential pulse polarography. The limit of determination is 4.2×10^–5 mol/l Co (2.5 mg/l). Linear calibration curves are obtained within the range of 1×10^–7 to 5×10^–6 mol/l cobalt without zinc and in the presence of 5×10^–3 mol/l Zn. The analytical method developed is suitable for the determination of cobalt in zinc plant solutions.

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Cobaltbestimmung in Gegenwart hoher Zinkkonzentrationen mit Hilfe der Differential-Puls-Polarographie