Ruthenium(II) bipyridine complexes bearing quinoline-azoimine (NN'N″) tridentate ligands: synthesis, spectral characterization, electrochemical properties and single-crystal X-ray structure analysis.

Four octahedral ruthenium(II) azoimine-quinoline complexes having the general molecular formula [Ru(II)(L-Y)(bpy)Cl](PF6) {L-Y=YC6H4N=NC(COCH3)=NC9H6N, Y=H (1), CH3 (2), Br (3), NO2 (4) and bpy=2,2'-bipyrdine} were synthesized. The azoimine-quinoline based ligands behave as NN'N″ tridentate donors and coordinated to ruthenium via azo-N', imine-N' and quinolone-N″ nitrogen atoms. The composition of the complexes has been established by elemental analysis, spectral methods (FT-IR, electronic, (1)H NMR, UV/Vis and electrochemical (cyclic voltammetry) techniques. The crystal structure of complex 1 is reported. The Ru(II) oxidation state is greatly stabilized by the novel tridentate ligands, showing Ru(III/II) couples ranging from 0.93-1.27 V vs. Cp2Fe/Cp2Fe(+). The absorption spectrum of 1 in dichloromethane was modeled by time-dependent density functional theory (TD-DFT).

Effects of various competing ligands on the kinetics of trace metal complexes of Laurentian Fulvic Acid in model solutions and natural waters.

The objective of this work was to study the effects of the following Ligands: Chelex-100, Dowex MAC-3 and Dowex 50WX-8 using Competing Ligand Exchange Method. This objective was achieved by investigating complex dissociation kinetics of trace metals: Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Mn(II) and Pb(II) of a well-characterized Laurentian Fulvic Acid (LFA) in model solutions and in a natural waters of Lake Heva (Québec, Canada). The effects of variation in the competing ligands (including their quantities) on the complex dissociation kinetics were quantitatively characterized by their first-order dissociation rate coefficients. The kinetic lability of the metal complexes varied with the metal-to-LFA ratio, as expected from the theory of metal complexes of the chemically and physically heterogeneous complexants, LFA. The general trend in the metal-binding by the above competing ligands was: Dowex 50WX-8>Chelex-100>Dowex MAC-3. However, no difference was found between the Dowex 50WX-8 and Chelex-100 for Cd(II), Zn(II), and Co(II). The results revealed the importance of the quantity of Chelex-100 as a competing ligand in the metal(II)-LFA complexation, on the dissociation kinetics of these complexes in model solutions. By developing Competing Ligand Exchange Method as an analytical technique, for studying the relative affinities of the above competing ligands for metals complexation in natural waters this work has made a substantial contribution to analytical chemistry.

Kinetic study of uranium speciation in model solutions and in natural waters using Competitive Ligand Exchange Method.

Kinetic speciation of uranium in model solutions containing uranium and humic acid (HA) and in natural waters has been investigated by Competitive Ligand Exchange Method (CLEM). In alkaline freshwaters, most of uranium species were uranium-carbonate species, which were labile in the CLEM experiment. The uranium speciation of every sample was characterized either as "labile" or "non-labile" uranium complexes depending on the dissociation rate coefficients of the complexes. The results showed that as the U(VI)/HA ratio was decreased, the dissociation rate coefficients decreased and the labile fraction decreased as well. When the U(VI)/HA ratio was 0.1, the labile fraction of the U(VI)-HA increased with increasing pH; however, there was no pH effect on the dissociation of U(VI)-HA complexes at lower U(VI)/HA ratios. Chelex-100 had some limitations in its use for the study of dissociation of U(VI)-HA complex at very low U(VI)/HA ratios. By developing an analytical method and procedure for quantitative determination of kinetic parameters for the dissociation of uranium-HA complexes in model solutions and natural waters, this work has made a substantial contribution to analytical chemistry.

Investigation of DGT as a metal speciation technique for municipal wastes and aqueous mine effluents.

This paper reports the results of an investigation on the performance of the Diffusive Gradient in Thin Films (DGT) Technique in speciation of metals in aqueous samples of municipal wastes and mine effluents. The DGT was assessed regarding its suitability for in situ determination of metal speciation in municipal wastes and aqueous mine effluents. As the thickness of the diffusive gel layer of the DGT was increased to 0.40, 0.80, and 1.60 mm, a decrease in the amount of accumulated metal mass was observed for most of the metals studied in all the effluent samples. However, the results were different from one field-study site to another. Effect of kinetics also was observed in the amount of accumulated metal mass by the DGT. The computer speciation code, Windermere Humic Aqueous Model (WHAM VI), was used to predict the metal speciation of Cd, Cu, Ni, Pb, Co, and Zn, and WHAM predictions were compared with those of the experimentally determined metal speciation by the DGT technique (free and labile metal ions). This comparison showed good similarities between the theoretically predicted WHAM VI values and the experimentally measured values by DGT. The DGT technique was found to be simple and useful for investigating chemical speciation of trace metals in aqueous samples of municipal wastes and aqueous mine effluents.

Simultaneous determination of speciation parameters of Cu, Pb, Cd and Zn in model solutions of Suwannee River fulvic acid by pseudopolarography.

There is a growing awareness of the importance of quantitative determinations of speciation parameters of the trace metals Cu, Zn, Cd and Pb in aqueous samples containing chemically heterogeneous humic substances, especially when they are present together, interacting with one another and competing for specific binding sites of the humic substances. Such determinations require fundamental knowledge and understanding of these complex interactions, gained through basic laboratory-based studies of well-characterized humic substances in model solutions. Since the chemical heterogeneity of humic substances plays an important role in the thermodynamics (stability) and kinetics (lability) of trace metal competition for humic substances, a metal speciation technique such as pseudopolarography that can reveal the special, distinctive nature of metal complexation is required, and it was therefore used in this study. A comparison of the heterogeneity parameters (Gamma) for Zn(II), Cd(II), Pb(II) and Cu(II) complexes in model solutions of Suwannee River fulvic acid (SRFA) shows that GammaCd>GammaZn>GammaPb>GammaCu, suggesting that SRFA behaves as a relatively homogeneous complexant for Zn(II) and Cd(II), whereas it behaves as a relatively heterogeneous complexant for Pb(II) and an even more heterogeneous complexant for Cu(II) under the experimental conditions used. The order of values of log K* (from the differential equilibrium function, DEF) for the trace metals at pH 5.0 follow the sequence: log K*Cu>log K*Pb>log K*Zn>log K*Cd. These results are in good agreement with the literature values. The results of this work suggest the possibility of simultaneously determining several metals in a sample in a single experiment, and hence in a shorter time than required for multiple experiments.

Kinetic speciation of nickel in mining and municipal effluents.

This study presents the results of kinetic speciation of nickel in undiluted mining and municipal effluents and effluents diluted with receiving freshwaters from the surrounding environment. The dilution ratios used for the dilution of the effluents were arbitrarily chosen, but were representative of the prevailing mining practices. The purpose of the this dilution was to mimic dilution with natural waters that result from dilution of the mining and municipal effluents with receiving freshwaters, so that this study would reveal environmental realities that are of concern to the managers and regulators of water resources. Ligand exchange kinetics using the competing ligand exchange method (CLEM) was studied using two independent techniques: graphite furnace atomic absorption spectrometry (GFAAS) with Chelex 100 resin as the competing ligand, and adsorptive cathodic stripping voltammetry (AdCSV) with dimethylglyoxime (DMG) as the competing ligand to determine the percentage of Ni metal released from Ni(II)-DOC complexes and the rate of dissociation of Ni(II)-DOC complexes. Using a sample containing a mixture of 30% Copper Cliff Mine effluent, 40% Sudbury municipal effluent and 30% Vermillion River water, both techniques gave results showing that the dilution of the effluent samples increased the percentage of nickel released from Ni(II)-DOC complexes. This increase in the release of nickel from the Ni(II)-DOC complexes may be of concern to managers and regulators of water resources. Agreement between the results of these two techniques has enhanced the validity of the competing ligand exchange method used by both techniques.

Kinetics of trace metal competition in the freshwater environment: some fundamental characteristics.

Freshwaters are recognized as dynamic systems that may be far-removed from equilibrium. A kinetic approach using the competing ligand exchange method with Chelex 100 as the competing ligand and inductively coupled plasmamass spectrometry to measure the dissociation kinetics was used to investigate the chemical speciation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) in model solutions of a well-characterized fulvic acid (Laurentian fulvic acid) and a freshwater sample collected from the Grand River (Ontario, Canada). The kinetic distribution of the metal species were quantitatively characterized by their first-order dissociation rate constants. This kinetic speciation approach has the advantage of providing an objective method for estimating the dissociation rate constants without any a priori assumptions about the number of kinetically distinguishable components or the shape of the distribution. Three factors were found to influence the kinetics of trace metal competition in the freshwater environment: (i) metal-to-ligand ratio, (ii) ionic potential (z2/r), and (iii) ligand field stabilization energy. The results illustrate the importance of considering the valence-shell electron configuration in predicting the kinetics of trace metal competition in the freshwater environment. The markedly slow dissociation kinetics of Ni(II) and Cu(II) species suggest that the usual equilibrium assumption for freshwaters may not be valid. This study has demonstrated the ability of the kinetic model to correctly predict the relative rates of trace metal reactions, indicating that the kinetic model provides a chemically significant description of the kinetic processes in natural waters.