Retention of long-chain acetylenic hydrocarbons on non-polar stationary phases

The retention indices of methyl and trimethylsilyl esters of octadeca-, eicosa- and tricosa-ynoic fatty acids containing acetylenic bonds were measured on non-polar stationary phase (dimethylsilicone with 5% phenyl groups). An unusually large increase in retention is observed for compounds containing conjugated and methylene interrupted acetylenic bonds. The additional increase in retention index as a result of the presence of one conjugated acetylenic bond is roughly equivalent to the retention increase caused by lengthening of the hydrocarbon chain for one carbon atom. The increase in retention for methylene interrupted bonds constitutes approximately 50% increase for conjugated triple bonds. A further increase in interruption substantially decreases the effect. Based on available literature data and the results of this work, the contributions of conjugated acetylenic and olefinic bonds, and methylene interrupted acetylenic bonds to retention were estimated.     

The correlation between the physical properties and structure of alcohols and their gas chromatographic behavior on polar and non-polar stationary phases : II. Branched-chain alcohols

Branched-chain alcohols with from one to eight carbon atoms have been analysed by gas chromatography using thermal conductivity and flame-ionization detectors. The specific retention volumes, V_g, and the retention indices relative to normal alcohols were determined for all the compounds, and the effects of the branching and of the position of the hydroxyl groups have been investigated. Boiling points, vapour pressures, molecular volumes were correlated with the measured retention values. The activity coefficients at infinite dilution and the normalized activity coefficients were calculated, and their influence on the separation is discussed. The results are compared with the behaviour of branched-chain halogenoalkanes on polar and non-polar stationary phases.     

Tetraalkoxyaluminates of nickel(II), copper(II), and copper(I)

The syntheses and structural details of tetraisopropoxyaluminates and tetra-tert-butoxyaluminates of nickel(II), copper(I), and copper(II) are reported. Within the nickel series, either Ni[Al(OiPr)4]2.2HOiPr, with nickel(II) in a distorted octahedral oxygen environment, or Ni[Al(OiPr)4]2.py, with nickel(II) in a square-pyramidal O4N coordination sphere, or Ni[(iPrO)(tBuO)3Al]2, with Ni(II) in a quasi-tetrahedral oxygen coordination, has been obtained. Another isolated complex is Ni[(iPrO)3AlOAl(OiPr)3].3py (with nickel(II) being sixfold-coordinated), which may also be described as a "NiO" species trapped by two Al(OiPr)3 Lewis acid-base systems stabilized at nickel by three pyridine donors. Copper(I) compounds have been isolated in three forms: [(iPrO)4Al]Cu.2py, [(tBuO)4Al]Cu.2py, and Cu2[(tBuO)4Al]2. In all of these compounds, the aluminate moiety behaves as a bidentate unit, creating a tetrahedrally distorted N2O2 copper environment in the pyridine adducts. In the base-free copper(I) tert-butoxyaluminate, a dicopper dumbbell [Cu-Cu 2.687(1) A] is present with two oxygen contacts on each of the copper atoms. Copper(II) alkoxyaluminates have been characterized either as Cu[(tBuO)4Al]2, {Cu(iPrO)[(iPrO)4Al]}2, and Cu[(tBuO)3(iPrO)Al]2 (copper being tetracoordinated by oxygen) or as [(iPrO)4Al]2Cu.py (pentacoordinated copper similar to the nickel derivative). Finally, a copper(II) hydroxyaluminate has been isolated, displaying pentacoordinate copper (O4N coordination sphere) by dimerization, with the formula {[(tBuO)4Al]Cu(OH).py}2. The formation of all of these isolated products is not always straightforward because some of these compounds in solution are subject to decomposition or are involved in equilibria. Besides NMR [copper(I) compounds], UV absorptions and magnetic moments are used to characterize the compounds.     

Synthesis of copper(II) and nickel(II) triazacycloalkane complexes

Summary Copper(II) and nickel(II) complexes of triazacycloalkanes (pqr-cy), with p, q, r = 2–6, have been prepared and characterized by means of electronic and i.r. spectroscopy, and by magnetic measurements. With nickel(II) mononuclear octahedral complexes [Ni(pgr-cy)₂](CI0₄)₂ are formed, but for copper(II) mononuclear octahedral complexes were obtained only for 222-cy and 223-cy. The other ligands gave copper(II) complexes of the type [Cu(pgr-cy)CI]CIO₄, [Cu(pgr-cy)OH]ClO₄, Or [Cu(pgr-cy)CI_1/2OH_1/2]ClO₄. The hydroxy complexes have low magnetic moments and binuclear hydroxy bridged structures are proposed.Ligand names: e.g. p = q = r = 2 is 1,4,7-triazacvclononane     

Salen and tetrahydrosalen nickel(II) and copper(II) complexes

The synthesis and characterisation of novel bis salen complexes, M(salenH2), N,N-bis-[5(1,1,3,3-tetramethyl- butyl)salicylidene]-1,2-diaminoethane complexes, (M=Ni or Cu), and the corresponding less studied, bis-tetrahydrosalen complexes, M[H2(salenH2)], N,N-bis-[2-hydroxy-5(1,1,3,3-tetramethylbutyl)benzyl]-1,2-diaminoethane complexes, (M=Ni or Cu), with a highly branched substitution pattern at C-5 of the benzene ring is described. The Schiff bases behave as dibasic tetradentate ligands. The tetrahydrosalen complexes show structural properties, chemical and thermal behaviour which is different from those of the corresponding salen complexes. The melting points and decomposition temperatures of these complexes were determined by d.s.c. and t.g.a.     

Thermodynamic evaluation of the interaction of fatty acid methyl esters with polar and non-polar stationary phases,based on their retention indices

Summary Kovát retention indices are used to determine the partial molar free energies of solution of 39 methyl esters of saturated (normal and branched), mono- and poly-unsaturated higher fatty acids in the non-polar phase Se-30 and the polar phase SILAR 5CP. Contributions of double bonds as a function of their number and position in the acid chain to the partial molar free energies of solution (G) are evaluated quantitatively. Linear equations are suggested for the calculation of G of any compounds from their retention indices measured in columns with SE-30 and SILAR 5CP.     

Elution behavior of polyethylene in polar mobile phases on a non-polar sorbent

Linear polyethylene standards in the range of 1-500 kg/mol, dissolved in 1,2,4-trichlorobenzene, were injected into a column packed with oligo(dimethylsiloxane) modified silica gel. Fifteen polar solvents (cyclohexanone, cyclohexylacetate, cyclohexanol, nonylalcohol, dimethylformamide, dimethyl sulfoxide, ethylene- and diethylene glycol monobutyl ether, benzylalcohol, hexylacetate, bis(2-ethyl-hexyl)phthalate, N,N-dimethylacetamide, propylene carbonate, dipropylene glycol and N-methyl-pyrrolidone) were evaluated as mobile phases. Depending on the type of mobile phase evaluated, different elution behaviors are observed for polyethylene: (1) polyethylene was eluted in the size exclusion mode, (2) polyethylene was eluted together with the sample solvent peak at constant elution volume, (3) polyethylene was partially or fully retained on the column. The retained polymer was easily removed from the column by injecting a small volume of trichlorobenzene. The use of ethylene glycol monobutyl ether as the mobile phase enabled separation of the polyethylene from polypropylene. In this case polypropylene is eluted in the size exclusion mode, while polyethylene is eluted at a constant elution volume or remains in the column.     

Reaction of copper(II) and nickel(II) ammoniates with ethanol-amines

Thermogravimetry combined with thermal gas titrimetry were used to study the ligand substitution reactions by mono- and diethanolamine in nickel(II) hexaamminochloride and copper(II) tetraamminosulfate. It has been shown that the reactions proceed in stages and the temperature intervals of the individual stages have been determined. The kinetics of the described reactions have also been studied at isothermal conditions. The E_a values of the reactions have been calculated on the basis of the data obtained. A reaction mechanism has been proposed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 6, pp. 745–749, November–December, 1990.     

Complex formation of copper(II) and nickel(II) with N-arylthiopicolinamides

The reactions of N-arylthiopicolinamides (HL) with copper(II) and nickel(II) ions in organic and aqueous-organic solutions were studied. On addition of HCl, the transformation of ML₂ complexes into M(HL)Cl₂ occurs, while the reverse reaction takes place under the action of amphoteric protic solvents. The structures of the isolated complexes were established by IR and UV spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1546–1550, September, 1993.     

Extraction of copper(II) and nickel(II) by nopinoquinone dioxime

In the research for a selective extractant for nickel a strained dioxime, β-nopinoquinone dioxime, has been studied in its extraction properties for copper(II) and nickel(II). Spectroscopic investigations (ESR and NMR) showed that both copper and nickel are extracted as a N,N-coordinated chelate. The extraction studies showed that the use of strained instead of aliphatic dioximes makes the extraction more convenient because of the higher extraction rate, but the selectivity for nickel above copper disappears.δ-nopinoquinone dioxime is easily converted into its furazan by treatment with 1N NaOH. This furazan is a rather weak ligand without significant extraction capacities.     

2-thiouracil-based cobalt(II), nickel(II) and copper(II) complexes

Summary Cobalt(II), nickel(II) and copper(II) complexes of 2-thiouracil and its arylazo derivatives were prepared. The elemental analysis suggest a range of 11, 21 and 13 stoichiometries. Electronic spectra and magnetic susceptibility measurements were used to infer the structures and the i.r. spectra of the ligands and their complexes to identify the type of bonding.     

Cobalt(II), nickel(II) and copper(II) complexes of bidentate bibenzimidazoles

Summary Complexes of cobalt(II), nickel(II) and copper(II) with novel bidentate bibenzimidazoles, [M(L-L)Cl₂], where L-L are methylenebis(1, 1-benzimidazole), methylenebis(2, 2-benzimidazole) and dimethylenebis(2, 2-benzimidazole) are described and characterized by different physical measurements. The four coordinate complexes have distorted tetrahedral or square coplanar structures. The bridging entity between the two donor groups apparently influences the ligand field strength and the ligands occupy a higher position than that of benzimidazole in the spectrochemical series.     

Chemisorption of copper(II) at zinc and cadmium dialkyldithiocarbamates: EPR and X-ray diffraction studies

Chemisorption of Cu²⁺ cations at zinc and cadmium dialkyldithiocarbamates was studied. According to EPR data, in the first step, the zinc and cadmium atoms are partially replaced by copper in the starting molecular structure to form heterobinuclear and heteropolynuclear complexes. In the second step, copper replaces up to 90 to 97% of the total number of the metal atoms, yielding binuclear and polynuclear copper(II) complexes. The possibility of the existence of heterobinuclear complexes in the individual state was demonstrated with [CuCd{S₂CN(C₂H₅)₂}₄] as an example. Its molecular and crystal structures were determined from X-ray diffraction data.     

Encapsulation of nickel(II) and copper(II) by a tetraazamacrocyclic ligand

A tetraazamacrocyclic ligand, L, containing six non-equivalent benzene rings, derived from the condensation of benzil with 1,2- diaminobenzene, has been isolated and its complexes [MLCl₂] (M = Ni²⁺ and Cu²⁺) prepared and characterized by elemental analysis, i.r., u.v.–vis., e.p.r. spectral studies, magnetic moments, redox potentials and conductivity measurements. The complexes have axially elongated octahedral geometries with two axial chlorines, and adopt the trans-configuration. These studies also indicate the covalent nature and the high-spin octahedral structure for these complexes. A cyclic voltammetric investigation reveals that the complexes exhibit a single one-electron redox couple, as anticipated for a copper(II) complex (Cu²⁺/Cu⁺) and a single two-electron redox couple for a nickel(II) complex (Ni²⁺/Ni⁰). The electrochemical processes are considered quasi-reversible. Antimicrobial activities of the ligand and the complexes have been tested against Bacillus megaterium and Candida tropicallis.     

Extraction of copper(II) and nickel(II) by long-chain aliphatic dioximes

In the search for a selective nickel extractant symmetric dialkyl dioximes have been studied in the extraction of copper and nickel ions from ammoniaca