Polarographic study of mixed ligand complexes of Pb(II) with carboxylate ions and imidazole

Mixed complexes of Pb(II) with some carboxylate ions, viz. tartrate (tart^2?), malonate (mal^2?) and citrate (citr^3?); and imidazole (im) have been studied polarographically at 25°C and at constant ionic strength μ = 2.0 (NaNO₃) and at pH 6. The polarographic reduction of the complexes in each case is reversible and diffusion-controlled. Pb(II) forms a single mixed complex with tartrate and imidazole, viz [Pb(tart)(im)] with stability constant log β₁₁ = 4.19; with mal^2? and im, three mixed complexes, [Pb(mal)(im)], [Pb(mal)(im)₂] and [Pb(mal)₂(im)]^2? with stability constants log β₁₁ = 4.3, log β₁₂ = 7.3 and log β₂₁ = 5.5 respectively are formed. With citr^3? and im a single mixed species, [Pb(citr)(im)]^? with stability constant log β₁₁ = 8.0 is formed. Various equilibria involved in the mixed systems have been discussed.     

Comparative study of hydroxo-fluoro and hydroxo-sulphido mixed ligand complexes of aluminum(III) and gallium(III)

The mixed ligand complex formation had been studied in the aluminate-fluoride, gallate-fluoride, aluminate-sulphide and gallate-sulphide systems by spectrophotometric as well as potentiometric methods using glass and sulphide selective electrodes. The formation of the species Al(OH)₃F^? and Ga(OH)₂S^? has been demonstrated and the equilibrium constants have been determined. Similar interaction could not be detected in the aluminate-sulphide and gallate-fluoride systems.The differences in behaviour of the metal ions to the characteristically hard fluoride and soft sulphide ligands can be interpreted in that the Ga³⁺ ion may form complexes with charged soft ligands too, its behaviour then differing from that of the typically hard Al³⁺ ion.     

Equilibrium study of the systems of aluminium(III), gallium(III) and indium(III) with mercaptoacetate, 3-mercaptopropionate and 2-mercaptobenzoate

Equilibrium studies were carried out by pH-potentiometry on the systems of aluminium(III), gallium(III) and indium(III) with mercaptoacetate (MerAc^2?), 3-mercaptopropionate (MerPr^2?) and 2-mercaptobenzoate (MerBe^2?). It was found that the complex-forming properties of the Al³⁺ ion towards these mercaptocarboxylic acid ligands differ from those of Ga³⁺ and Al³⁺. Under the conditions of the study, Al³⁺ forms only hydroxo complexes, while Ga³⁺ and In³⁺ form relatively stable complexes involving the simultaneous coordination of the carboxylate and the deprotonated mercapto group. In all cases the equilibrium systems can be described without the assumption of polynuclear complexes. The complexes Ga(MerAc)₂ and Ga(MerBe)₂ show marked stability; this was interpreted in terms of back-coordination and of interaction between the d¹⁰ electrons of the Ga³⁺ ion and the empty d orbitals of the S donor atom. Complexes of composition ML_i are not formed in the Ga³⁺-MerPr^2? system; this points to the importan roles of the number of atoms in the chelate ring and the higher stability of the Ga(III)-hydroxo complexes.     

Polarographic study of Sn(IV) chloride-pyridine N-oxide complexes in acetonitrile

Polarograms recorded of Sn(IV) chloride in acetonitrile in the presence of controlled quantities of each of nine substituted pyridine N-oxide ligands demonstrated the formation of stable and soluble complexes with a stoichiometry dependent upon the nature and position of the ring substituent. The polarographic data associated with each complex and the free ligands are used to substantiate a proposed bonding model which explains the dependency of the complex formula on the ligand structure. The salt SnCl₄·5H₂O was employed as a source of Sn(IV) and the complete polarographic behaviour of this salt in acetonitrile is described as a basis for the interpretation of complex reduction behaviour.     

Characterization of Cr(III)-Zr(IV) mixed and Sn(II) doped hydrous oxides

Surface and structural properties of chromium-zirconium mixed and Sn(II)doped hydrous oxide gels have been compared with chromium oxide hydrate gel by the use of thermal analysis, IR spectroscopy, X-ray diffraction, electron microscopy and magnetic measurements. The mixed and doped oxide gels were found to have a hexagonal close packed stacking of O, OH and H₂O ligands with chromium ions distributed in octahedral sites with little degree of order among them. The microstructure of the gels are characterized by the presence of large aggregates of chromium hydroxides, fine granular sheets due to HCrO₂ phase and Cr(OH)₃ microcrystallites. Magnetic susceptibility measurements indicate anti-ferromagnetic behaviour of these gels.     

Polarographic study of dioxo-uranium(VI)-8-hydroxyquinoline-succinate system and thermodynamic parameters

The dioxo-uranium(VI)-8-hydroxyquinoline-succinate system has been studied polarographically at constant ionic strength (μ = 0.6 M KCl) in aqueous alcohol (7 : 3) at different temperatures. The reduction of the simple and mixed complexes is reversible and diffusion controlled. The DeFord-Hume and Schaap-McMaster methods have been applied in the determination of composition and stability constants of the simple and mixed complexes respectively. The thermodynamic parameters ΔG, ΔH and ΔS have also been calculated.     

Alkylenedithiophosphate derivatives of arsenic(III), antimony(III) and bismuth(III)

Tris(alkylenedithiophosphates) of arsenic(III), antimony(III) and bismuth(III),

have been synthesized by the reactions of alkylenedithiophosphoric acids with metal oxides and chlorides and of their ammonium salts with metal chlorides in suitable solvents. Mixed chloride alkylenedithiophosphates of arsenic(III) and antimony(III),

have been obtained by the reactions of metal chlorides with ammonium alkylenedithiophosphates at 1 : 1 and 1 : 2 molar ratios or alternatively by the co-disproportionations reactions of metal chlorides with metal tris(alkylenedithiophosphates) at different (2 : 1 and 1 : 2) molar ratios. These new compounds have been characterized by elemental analyses, molecular weight measurements and spectroscopic (IR, and ¹H and ³¹P NMR) data. Chelated structures with bidentate alkylenedithiophosphate groups have been proposed for all these derivatives.     

Allyl complexes of dicyclopentadienyl-niobium(III) and -tantalum(III)

The synthesis and the properties of the complexes Cp₂TaCl₂, Cp₂M(allyl), Cp₂M(1-methylallyl) and Cp₂M(2-methylallyl) with M  Nb, Ta are described. The complex Cp₂TaCl₂ has one unpaired electron per tantalum atom, while the allyl complexes are diamagnetic. The IR and PMR spectra indicate that the allyl group is π-bonded to the metal. The mass spectra of the complexes are discussed; the thermal stability of the Cp₂Nb- and Cp₂Ta-(allyl) complexes was investigated by differential thermal analysis. The properties of the niobium and tantalum complexes are compared with those of the corresponding titanium complexes.     

Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution—10. A potentiometric study of aluminium(III) pyrocatecholates and aluminium(III) hydroxo pyrocatecholates in 0.6 M Na(Cl)

Equilibria between aluminium(III), pyrocatechol (1,2-dihydroxybenzene, H₂L) and OH⁻ were studied in 0.6 M Na(Cl) medium at 25°C. The measurements were performed as emf titrations (glass electrode) within the limits 1.5 ≤ − log[H⁺] ≤ 9; 0.0005 ≤ B ≤ 0.015 M; 0.006 ≤ C ≤ 0.03 M and 2 ≤ C/B ≤ 30 (B and C stand for the total concentrations of aluminium(III) and pyrocatechol respectively). All data can be explained with a main series of complexes: A1L⁺, log β_−2,1,1 = − 6.337 ± 0.005; A1L₂⁻, log β_−4,1,2 = −15.44 ± 0.017 and A1L₃³⁻, log β_−6,1,3 = − 28.62 ± 0.024 together with two minor species: Al(OH)L₂²⁻, log β_−5,1,2 = − 23.45 ± 0.079 and Al₃(OH)₃L₃, log β_−9,3,3 = − 29.91 ± 0.066. Of the two, the latter probably is a type of average composition complex principally occurring at low C/B quotients. The first acidity constant for pyrocatechol as determined in separate experiments is log β_−1,0,1 = − 9.198 ± 0.001. The standard deviations given are 3σ(log β p,q,r). Data were analyzed with the least squares computer program LETAGROPVRID. In a model calculation using kaolinite as solid phase, we compared the complexation ability of this system with that of the system Al³⁺-OH⁻-salicylic acid, reported earlier in this series.     

Improved syntheses of chlorodicyclopentadienyl derivatives of scandium(III), titanium(III) and vanadium(III)

An improved synthesis of chlorodicyclopentadienyl derivatives of scandium(III), titanium(III) and vanadium(III) has been developed by the reaction of thallium cyclopentadienide with the appropriate anhydrous metal trihalides.     

A study of some reactions of acetylacetonatobis(ethylenediamine)cobalt(III) ion in sodium hydroxide solution

The reactions of acetylacetonato cobalt (III) ion in sodium hydroxide solutions have been studied spectrophotometrically over a range of temperatures and hydroxide ion concentrations. The activation enthalpy, ΔH^≠ was 70.6 kJ mol^?1 and the activation entropy, ΔS^≠ was ? 119 JK^?1mol^?1, with a rate law of k_obs = k₂ [OH^?]². A mechanism involving initial de-chelation of the acetylacetone ligand is suggested. The rate of exchange of methyl hydrogen of the acetylacetone ligand was studied, using proton nuclear magnetic resonance. The rate law was k_obs = k [OH^?]. Initial de-chelation is also suggested as a mechanism for this process. The ¹³C nuclear magnetic resonance spectrum of the complex is reported.     

Circularly polarized luminescence studies of the adducts formed with mix-ligand Eu(III) β-diketone complexes and dimethyl sulfoxide or N,N-dimethyl formamide

The adducts formed by Eu(DK)₂(CDK) and Eu(DK)(CDK)₂ [DK = achiral β-diketone ligand, and CDK = chiral β-diketone ligand] with either dimethyl sulfoxide (DMSO) or N,N-dimethyl formamide (DMF) have been studied by means of circularly polarized luminescence spectroscopy. While extremely strong stereoselective effects had been observed in earlier studies involving Eu(CDK)₃ adducts, analogous phenomena were found to be much smaller in the mixed-ligand compounds. These observations imply that steric interactions involving bulky camphorato ligands are significantly greater than those involving the achiral (and planar) β-diketone ligands.     

Synthesis and characterization of diethylphosphino Ga(III) and In(III) complexes with covalent metal-phosphorus bonds

The covalent derivatives [Et₂M-PEt₂]₃ (M = Ga, In) have been prepared from Lewis acid-base complexes, R₃M.PHEt₂, by alkane elimination and characterized by elemental analyses, IR, ¹H and ³¹P NMR spectroscopy. Features of the mass spectra reveal a trimeric form and the strength of the [M-P]_n ring. For the compound [ClMeGa-PEt₂]_n, spectral data are consistent with a weakening of the [Ga-P]_n chain, in good agreement with the pyrolysis results.     

Kinetics of the aquation of cis-chlorocyanobis(2,2′-bipyridine)cobalt(III) and cis-chlorocyanobis(1,10-phenanthroline)cobalt(III) cations

We have studied the kinetics of aquation of cis-chlorocyanobis(2,2′-bipyridine)Co(III), and cis-chlorocyanobis(1,10-phenanthroline)Co(III) cations, and determined activation parameters, in order to compare the labilities of these cations with the lability of the analogous compounds containing ethylenediamine and other non-participating ligands such as Cl^? and NO₂^?.     

ESR study on photoreaction of formato complex of europium(III) in HCOOH-HCOONa buffer solution

Matrix isolation ESR study showed that the ligated HCCO^? ion was decomposed into H⁺ and ·COO^? radical anion through CTTM process at λ = 254 nm, by contrast, ·CH₃ radical and CO₂ were produced from CH₃COO^? ligand. In order to explain the photo- and related reactions in the liquid solution, a proposal is made for a cyclic scheme conjugated with the photo-decomposition of the complex. The cycle consists of three steps; photo-reduction of H⁺ by Eu²⁺, radical alternation from ·H to ·COO^?, and oxidation of ·COO^? by Eu³⁺.     

Cationic dihydridoiridium(III) complexes of nitriles

The reaction of [IrL(CO)(PPh₃)₂]ClO₄ (PPh₃ = triphenylphosphine) with H₂ produces new cationic dihydridoiridium(III) complexes of nitriles (L), [Ir(H)₂L(CO)(PPh₃)₂]ClO₄ [L = CH₃CN (1), CH₃CH₂CN (2), CH₃CH₂CH₂CN (3) and C₆H₅CN (4)], where nitriles are coordinated through the nitrogen atom. Proton NMR spectral data for complexes 1–4 suggest that the two hydrides in each complex are cis to each other and trans to CO and nitrogen (nitrile), and the two PPh₃ are trans to each other.     

A polarographic study of the mixed complexes of Pb(II) with oxalate and malonate ions

The coordinated mixed Pb(II)-oxalate-malonate system has been polarographically studied in aqueous medium. The ionic strength has been maintained constant at μ = 1.0 by using NaClO₄. Application of the Schaap and McMasters method detected only the existence of the [Pb-ox-mal]_2? complex, the overall stability constant of which was β₁₁ = 4.1 x 10⁵.The various coordination equilibria are discussed on the basis of statistical aspects.     

Inner-sphere oxidation of iron(II) by tris(malonato)cobaltate(III)

The kinetics of oxidation of Fe²⁺ by [Co(C₃H₂O₄)₃]^3? in acidic solutions at 605 nm showed a simple first-order dependence in each reactant concentration. The second-order rate constant dependence on [H⁺] is in accordance with eqn (i) k₂ = k′₂ + k₃[H⁺] (i) where k′₂ and k₃ have values of 73.4 ± 14.0 M ^?1 s^?1 and 353 ± 41 M^?2 s^?1, respectively, at 1.0 M ionic strength (NaClO₄) and 25°C. At 310 nm the formation and decomposition of an intermediate, believed to be [FeC₃H₂O₄]⁺, was observed. The increase in the rate of oxidation with increasing [H⁺] was interpreted in terms of a “one-ended” dissociation mechanism which facilitates chelation of Fe₂₊ by the carbonyl oxygens of malonate in the transition state.     

Evidence for absence of an inverted region for Ru(III)-Ti(III) outer-sphere electron-transfer reaction

A lower limit of 10⁸ M^?1 s^?1 was obtained for the 2nd-order rate constant at 25°C for the reduction of Ru(bpy)₃³⁺ by Ti(III) in an aqueous medium of ionic strength 1.0 M and pH range 0–2. The theoretical implications of this result are discussed.