Liquid-liquid extraction: A graphical method for equilibrium stage calculations for quaternary systems

Ruiz Beviá, F., Prats Rico, D. and Marcilla Gomis, A.F., 1984. Liquid-liquid extraction: a graphical method for equilibrium stage calculations for quaternary systems. Fluid Phase Equilibria, 15: 257-265.A very simple graphical method for stage calculations has been developed for quaternary systems. The calculation method is based on the equilibrium representation method proposed by Ruiz and Prats (1983a), and requires only two graphs for solution of the material balances. The method is based completely on experimental data and does not require any simplifying hypotheses.     

A new method for the trifluoromethylation of aromatics

A new method is discribed for introducing a CF₃-group, by a single-step synthesis, into aromatic compounds. This trifluoromethylation is done by means of a mixture consisting of HF/CCL₄ and the aromatic compound. The reaction is thought to be of a Friedel-Crafts type and limited to aromatics which are not substituted by electron withdrawing groups.     

A reaction-rate method for the determination of thiocyanate,based on its inhibitory effect on the iodate-hypophosphite reaction

An automatic spectrophotometric reaction-rate method is described for the determination of thiocyanate in aqueous solutions, based on its inhibitory effect on the iodate-hypophosphite reaction. The time required for the reaction to proceed between two pre-determined levels is measured automatically and related directly to the thiocyanate concentration. The recommended reaction-rate method is fast, simple, sensitive, accurate (to 2%) and precise (1.7%, relative standard deviation). The useful analytical range of concentrations of thiocyanate is 4 × 10^?5 to 5 × 10^?4M. Maximum tolerable amounts of interfering ions are also presented.     

Charge transfer complexes: synthesis of 3,5-naphtho-1-telluracyclohexane,a new electron donor

The reaction of 1,8-bis(bromomethyl)naphthalene with tellurium powder and sodium iodide gives the orange 3,5-naphtho-1-telluracyclohexane-1,1-diiodide which on reduction gives 3,5-naphtho-1-telluracyclohexane. Reaction of 1,2,4,5-tetrakis(bromomethyl)benzene with elemental tellurium and sodium iodide gives the yellow 1,2,4,5-bis(diiodotelluracyclopentano)bezene, which upon reduction affords a highly insoluble material. 3,5-Naphtho-1-selenahexane has been prepared in excellent yield by treating sodium selenide with 1,8-bis(bromomethyl)napthalene. Charge-transfer complexes of the telluride and of telluracyclohexane and tellura-cyclopentane are reported.     

Transition metal complexes with 1-methyl-4,4-dimercaptopiperidine

The syntheses of Co(AH₂)₂X₂ (AH₂ = 1-methyl-4, 4-dimercaptopiperidine, X = Cl Br, I, acetate, propanate, perchlorate, nitrate and sulphate), M(AH₂) Cl₂ (M = Cd, Zn) are described. According to IR and UV-visible data it seems most probable that the aminogem-dithiol (AH₂) coordinates Co via both sulphur atoms, but Zn and Cd via one sulphur. A square pyramidal geometry about Co and a tetrahedral geometry about Zn and Cd are proposed. In no case has coordination via nitrogen been found. Strong X-H…N hydrogen bonds have been observed in most of these complexes.     

A convenient synthetic route to new bis(arenediazo) complexes of molybdenum and tungsten

Complexes of the type [(C₅H₅)Mo(N₂Ar)(N₂Ar′)(PPh₃)] [PF₆] have been prepared and shown to be useful starting materials for the synthesis of a variety of neutral, cationic or anionic compounds containing [cis-Mo(N₂Ar)(N₂Ar′)]²⁺ units.     

A new method for the preparation of Ru(IV) in non-complexing acid medium: Evidence for tetrameric Ru(IV)

A new method for the preparation of Ru(IV) in acid solutions is described. This method, avoiding the preparation of the highly reactive RuO₄, is based on the stoichiometric oxidation of Br^? ion of K₂RuBr₆ by BrO₃^? ion. Easy to control and reproducible the process leads to solutions of a well-known composition consisting of the tetrameric Ru(IV) ion.     

A new example of ligand-to-metal electron-transfer process : one-electron reduction products of nickel(II)-tetradentate schiff base complexes

The reduction of three nickel(III) complexes involving two symmetrical N,N′-ethylenebis (acetylacetoneiminato) and N,N′-ethylenebis (salicylideneiminato) and one non-symmetrical N,N′-ethylene (acetylacetoneiminatosalicylideneiminato) and Schiff bases has been investigated by electrochemistry and ESR spectroscopy. In all cases, exhaustive reduction results in the formation of nickel(I) complexes. However, ESR data support the formation of a nickel(II)-stabilized ligand radical species at the early stage of the reduction of the non-symmetrical Schiff base complex.     

Studies on the intermolecular interactions of metal chelate complexesVIII: On the interactions of dithiocarbamato-copper(II) and -copper(I) complexes with haloalkanes

The interaction of Cu(II)(dtc)₂ and Cu(I)(dtc) complexes with haloalkanes were studied by the EPR method. It was found that the Cu(II)(dtc)₂ complex reacted with haloalkanes only in the presence of weak Lewis bases which formed adducts with it. The intermediate reaction product is the mixed-ligand complex Cu(II)(dtc)X_n (X = Cl, Br, n = 1 or 2); the final products being CuX₂B_n (B = Lewis bases, n = 1 or 2) and unstable resin-like residue. Cu(I)(dtc) reacted with haloalkanes without any promoters giving the mixed-ligand complex Cu(II)(dtc)X_n as product. Free radicals were detected in the reaction of Cu(I)(dtc) using the method of “radical scavenger” and were not found in the reaction of Cu(II)(dtc)₂. The reported results confirmed one of the two reaction mechanisms proposed in the previous studies. The role of the solvent on the EPR parameters of the mixed-ligand Cu(II)(dtc)X complex is also discussed.     

Peaceful pyrolysis-a novel method for the decomposition of metal-perchlorate complexes of organic ligands

Perchlorate complexes of vanadium(IV), iron(III), dysprosium, yttrium, copper(II) and nickel with the organic ligands dimethyl sulphoxide, antipyrine, 4-aminoantipyrine, 4-(2-hydroxynaphthyl)-azoantipyrine, and 4-(2,4-dihydroxyphenyl)azoantipyrine have been prepared and analysed for their metal content after decomposition by a non-explosive pyrolytic technique, viz. heating with ammonium chloride. The results obtained agree with those obtained by the standard methods. This pyrolytic technique is found to be very convenient, rapid and accurate.     

The weiss constant: A probe for the molecular packing of monomeric copper(II) complexes?

Magnetic properties of the complexes Cu(pn)₂WO₄1.8H₂O, Cu(pn)₂I₂, Cu(pn)₂Br₂ 1.6H₂O and Cu(pn)₂Cr₂O₇ (ph = 1,2-diaminopropane) have been studied by ESR, magnetic balance (Gouy method) and PA techniques. Curie constants C were obtained from ESR spectra, temperature independent paramagnetism N∝ from PA spectra, and Weiss constants from magnetic susceptibility data. Isotropic factors r were calculated, describing reduction of the orbital angular momentum and the spin-orbit coupling constant from their free-ion values. From the measured crystal g values we conclude that there is axial elongation in all the coordination polyhedra, corresponding to the ground state d_x2-y2. The different line shapes in the ESR spectra depend on the alignment of the pseudo-tetragonal axes, induced by the counterion. The counterions have a clear effect on both the magnetic parameters and the reduction factors. The alignment of the pseudotetragonal axes is also reflected in the value of the Weiss constant. A correlation is proposed between the Weiss constant and molecular packing.     

Alkali metal complexes: Complexes of alkali metals with quinaldinic acid

Complexes having the general formula ML.HL, where M = Na, K, Rb or Cs and HL = quinaldinic acid, have been obtained. The isolation of adducts in the solid state appeared to be favoured by increase in atomic radius, and hence decrease in ionisation potential of the metal. Attempts to synthesise similar adducts of picolinic acid N-oxide and quinaldinic acid N-oxide did not succeed. Complexes have been characterised by elemental analyses, thermal, IR spectral and solution studies. Our findings suggest that pK value of the ligands cannot be regarded a dominant factor in the synthesis and isolation of alkali metal complexes.     

Synthesis,physicochemical properties and voltammetric characterization of some new Fe(III) complexes with semicarbazone-based ligands

Several bis(ligand) octahedral complexes of iron(III) with salicylaldehyde semi-, thiosemi-, and S-methylthiosemi- carbazones have been synthesized and characterized by elemental analysis, conductivity and magnetic measurements, electronic and IR spectra, as well as by linear sweep and cyclic voltammetry. General procedures for the syntheses of all types of complexes have been established, giving better defined reaction conditions. Physicochemical properties of the novel complexes have been related to those of the already known compounds of the same type.     

Organotellurium cations: Organotellurium perchlorates and their complexes with Lewis bases

Solutions of diorganotellurium(IV) diperchlorates R₂Te(ClO₄)₂ (where R = Ph, p-CH₃OC₆H₄, R₂Te = $\text{C}{}_4\text{H}{}_8\text{Te}$) may be prepared by the reaction of R₂TeCl₂ and AgClO₄ or by the reaction of diorganyltelluroxide with excess of 70% HClO₄.IR and conductivity data indicate that Ph₂Te(ClO₄)₂ possesses covalently bonded perchlorate groups in solution. Interaction of the freshly prepared solutions with Lewis bases affords cationic complexes of the types [R₂Te(ClO₄)(L)][ClO₄] and [R₂Te(L)₂][ClO₄]₂ which have been characterised by IR elemental analyses and conductivity measurements.     

A new synthetic procedure for the preparation of pyridinium tetrafluoroborate and hexafluorosilicate

Pyridinium tetrafluoroborate (C₅H₅NHBF₄) and pyridinium hexafluorosilicate [(C₅H₅NH)₂SiF₆] have been prepared in good yields and high purity by the reaction of pyridinium poly(hydrogen fluoride) with oxides and acids of boron and silicon respectively. The salts have been characterised by melting points, IR, ¹H and ¹⁹F NMR spectroscopy and chemical analysis.     

Esca studies on the structure of amorphous addition complexes of tin dichloride with aromatic schiff bases

The ESCA characterization of three similar new amorphous addition complexes of tin dichloride with tetradentate aromatic Schiff bases has been carried out. The results support the previously proposed ionic structure.     

Coordination chemistry of new sulphur containing ligands—26. Eight coordinate vanadium(IV) and molybdenum(IV) complexes of 2-amino-1-cyclopentenedithiocarboxylate1

The new difunction ligand, 2-amino-1-cyclopentenedithio-carboxylate(L), was prepared and its coordination chemistry examined to gain further insight into the reactivity of “aromatic” dithio type ligands. Reaction with MoCl₄py₂ and VOSO₄, led to the surprising eight coordinate products ML₄. The sp² hybridization of the ring carbon to which the CS₂ moiety is bonded apparently yields a pseudo-aromatic effect on the reactivity of this ligand. The physical properties of these new compounds are discussed.     

Study of the complexes of Np(V) with organic ligands by solvent extraction with TTA and 1, 10-phenanthroline

Complex formation constants of Np(V) with 22 organic ligands, 7 hydroxycarboxylic acids, 4 dicarboxylic acids, 4 aminocarboxylic acids, 3 pyridinecarboxylic acids, 8-hydroxyquinoline-5-sulfonic acid, IDA, NTA and EDTA, have been determined in 1M NaClO₄ at 25°C by using the solvent extraction method with TTA and 1, 10-phenanthroline. The factors influencing the stabilities of Np(V) complexes are discussed in connection with the linear structure of NpO₂⁺.     

Mixed metal PtxMyLz complexes of L = 1-methyluracil and 1-methylthymine: Preparation and spectroscopic studies

The reactions of cis-(NH₃)₂PtL₂ (L = 1-MeT or 1-MeU, the anions of 1-methylthymine or 1-methyluracil respectively) in water with various salts of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) or Ag(I) have produced 14 new heteronuclear complexes of the general types: cis-[(NH₃)₂PtL₂ML₂Pt(NH₃)₂]X_n·mH₂O or cis-(NH₃)₂PtL₂MX_n·mH₂O, and also with silver(I) perchlorate a complex of stoichiometry cis-{(NH₃)₂Pt(1-MeU)₂}₂· 3AgClO₄·6H₂O. Comparisons are made with previously reported heteronuclear species derived from cis-(NH₃)₂PtL₂ and factors influencing the type of heteronuclear complex formed are discussed, particularly the versatility of binding patterns with Ag(I). A tetranuclear structure is suggested for the compound of stoichiometry cis-(NH₃)₂Pt(1-MeU)₂·FeSO₄·3H₂O involving iron(II) ions linked by sulphate bridges. The electronic spectra of the trinuclear complexes cis-[(NH₃)₂Pt(1-MeU)₂M(1-MeU)₂Pt(NH₃)₂] (NO₃)₂·mH₂O (M = Fe, Co or Ni) are reported. They show that the trans-MO₄Pt₂ geometry results in a very severely trans-elongated ligand field about the central metal ion, M. This conclusion is supported by the Mössbauer spectrum in the case of the iron(II) complex. The X- and Q-band EPR spectra of the Fe(III) analogue are also reported.     

Chemistry of iron complexes—III. X-ray diffraction,ESR and other spectral studies of new iron(II) and iron(III) complexes with tri-p-tolylarsine oxide

Reactions of iron(II) and iron(III) salts with tri-p-tolylarsine oxide(L) in suitable organic solvents yield complexes of formulas: (i) [FeL₂Cl₂(OH₂)₂] [FeCl₄].2H₂O, [FeL₂Br₂] [FeBr₄].2H₂O; (ii) [Fe(NCS)₃L₂].H₂O; (iii) [FeL(O₂ClO₂)₂(OH₂)] (ClO₄).0.25C₆H₆; (iv) [FeL₃I] [FeI₃].H₂O and (v) [Fe(CO)₃LI]I. Characterization has been done through elemental analyses, IR, far IR, ESR, and reflectance spectra, molar conductance, magnetic moments, t.g.a. and X-ray diffraction (powder) data. The species [FeL₂Cl₂(OH₂)₂]⁺, [FeL₂Br₂]⁺, [Fe(NCS)₃L₂], [FeL(O₂ClO₂)₂OH₂]⁺, [FeL₃I]⁺ and [Fe(CO)₃LI]⁺ have been assigned trans-octahedral, trans-square planar, trans-trigonal bipyramid, trans-octahedral, tetrahedral and cis-trigonal bipyramid structures respectively.