Aqueous metal complexes involved

Overview of the Metal Complexes Involved in Aqueous Catalysis... 

The pressure jump relaxation technique has first been applied with conductometric readout to study the formation of metal complexes involving Be2+, Al ", Ga ", In ", Ni , and Fe , for which the reaction can be described by the Eigen-Tamm mechanism. These measurements have been summarized before. Recently examples have been found where in the case of bidentate ligands the formation of both.monOdentate and bidentate complexes could be observed separately [l3l. Since the different complexes form at different rates, rate as well as equilibrium constants are obtained. In the case of carboxylate ligands it is difficult or even impossible to obtain these equilibrium constants by static measurements. Besides aqueous and nonaqueous solutions also mixed solvents have been used for the investigation of metal complexation [14,15]. In the case of the Be /S0 system which shows a single relaxation effect in aqueous solution, up to five different relaxation effects are observed in mixed solvents, which refer to different composition of the solvation shell of the cation. 

The most common oxidation state of niobium is +5, although many anhydrous compounds have been made with lower oxidation states, notably +4 and +3, and Nb can be reduced in aqueous solution to Nb by zinc. The aqueous chemistry primarily involves halo- and organic acid anionic complexes. Virtually no cationic chemistry exists because of the irreversible hydrolysis of the cation in dilute solutions. Metal—metal bonding is common. Extensive polymeric anions form. Niobium resembles tantalum and titanium in its chemistry, and separation from these elements is difficult. In the soHd state, niobium has the same atomic radius as tantalum and essentially the same ionic radius as well, ie, Nb Ta = 68 pm. This is the same size as Ti ... 

Arsonium salts have found considerable use in analytical chemistry. One such use involves the extraction of a metal complex in aqueous solution with tetraphenyiarsonium chloride in an organic solvent. Titanium(IV) thiocyanate [35787-79-2] (157) and copper(II) thiocyanate [15192-76-4] (158) in hydrochloric acid solution have been extracted using tetraphenyiarsonium chloride in chloroform solution in this manner, and the Ti(IV) and Cu(II) thiocyanates deterrnined spectrophotometricaHy. Cobalt, palladium, tungsten, niobium, and molybdenum have been deterrnined in a similar manner. In addition to their use for the deterrnination of metals, anions such as perchlorate and perrhenate have been deterrnined as arsonium salts. Tetraphenyiarsonium permanganate is the only known insoluble salt of this anion. 

The processes of complex-ion formation referred to above can be described by the general term complexation. A complexation reaction with a metal ion involves the replacement of one or more of the coordinated solvent molecules by other nucleophilic groups. The groups bound to the central ion are called ligands and in aqueous solution the reaction can be represented by the equation ... 

By contrast, the acidity of the metal salts used in these cements has a less clear origin. All of the salts dissolve quite readily in water and give rise to free ions, of which the metal ions are acids in the Lewis sense. These ions form donor-acceptor complexes with a variety of other molecules, including water, so that the species which exists in aqueous solution is a well-characterized hexaquo ion, either Mg(OH2)g or Zn(OH2)g. However, zinc chloride at least has a ternary rather than binary relationship with water and quite readily forms mixtures of Zn0-HCl-H20 (Sorrell, 1977). Hence it is quite probable that in aqueous solution the metal salts involved in forming oxysalt cements dissolve to generate a certain amount of mineral acid, which means that these aqueous solutions function as acids in the Bronsted-Lowry sense. 

Some of the types of equilibria involved in the unit operations separation and concentration are listed in the introduction, Section 9.17.1. Those which depend most on coordination chemistry, and for which details of metal complex formation are best understood, are associated with hydrometallurgy. Once the metal values have been transferred to an aqueous solution, the separation from other metals and concentration can be achieved by one of the following processes.3... 

In aqueous solution, a metal complex is enclosed by several solvation spheres involving many solvent molecules. As recently shown, for mechanistic studies a reduced coordination sphere is sufficient (157,159), and therefore here inclusion of a third solvent molecule is sufficient. Addition of a third water molecule results in the exothermic formation of [Be(H20)2(L)--H20] and [Be(H20)2(LH)--H20]+, where the third hydrogen-bonded... 

The sol-gel entrapment of the metal complexes [Ru(p-cymene)(BINAP)Cl]Cl and the rhodium complexes formed in situ from the reaction of [Rh(COD)Cl]2 with DlOP and BPPM has been reported by Avnir and coworkers [198]. The metal complexes were entrapped by two different methods the first involved addition of tetramethoxysilane to a THF solution of the metal complex and triethylamine, while the second method was a two-step process in which aqueous NH4OH was added to a solution of HCl, tetramethoxysilane and methanol at pH 1.96 followed by a THF solution of the appropriate metal complex. The gel obtained by each method was then dried, crushed, washed with boiling CH2CI2, sonicated in the same solvent and dried in vacuo at room temperature until constant weight was achieved. Hydrogenation of itaconic acid by these entrapped catalysts afforded near-quantitative yields of methylsuccinic acid with up to 78% e.e. In addition, the catalysts were found to be leach-proof in ethanol and other polar solvents, and could be recycled. 

This account is concerned with the rate and mechanism of the important group of reactions involving metal complex formation. Since the bulk of the studies have been performed in aqueous solution, the reaction will generally refer, specifically, to the replacement of water in the coordination sphere of the metal ion, usually octahedral, by another ligand. The participation of outer sphere complexes (ion pair formation) as intermediates in the formation of inner sphere complexes has been considered for some time (122). Thermodynamic, and kinetic studies of the slowly reacting cobalt(III) and chromium(III) complexes (45, 122) indicate active participation of outer sphere complexes. However, the role of outer sphere complexes in the reactions of labile metal complexes and their general importance in complex formation (33, 34, 41, 111) had to await modern techniques for the study of very rapid reactions. Little evidence has appeared so far for direct participation of the... 

Hydrometallurgical methods4,5 use reactions in aqueous solution (often involving metal complex formation) to concentrate and/or separate the metal ions of interest. A commercially important example is the heap leaching of low-grade copper ores with acid. 

The previous examples involve reduction (hydrogenation) of organic molecules, but transition metal complexes can also catalyze oxidation. For example, the Wacker process, which has been widely used to convert ethylene to acetaldehyde, depends on catalysis by palladium(II) in the presence of copper(II) in aqueous HC1. The role of the copper chloride is to provide a means of using air to reoxidize the palladium to palladium(II). Once again, Zeise-type coordination of the ethylene to the metal center is believed to be involved ... 

The term Counter Phase Transfer Catalysis (CPTC) was coined by Okano214,215 to describe biphasic reactions catalysed by water soluble transition metal complexes which involve transport of an organic-soluble reactant into the aqueous phase where the catalytic reaction takes place. Similarly, Mathias and Vaidya564,565 gave the name Inverse Phase Transfer Catalysis to describe this kind of biphasic catalysis which contrasts with classical Phase Transfer Catalysis where the reaction occurs in the organic phase and does not involve formation of micelles.389,564... 

Homogeneous catalysis by transition metal complexes almost always involves processes in which product-catalyst separation and catalyst recycling are important issues. For years, researchers have worked to find effective ways to isolate metal-complex catalysts in phases separate from those containing the catalyst, usually by anchoring the metal complex to a solid surface. As summarized by Driessen-Holscher, it is now evident that the method that has met with most practical success in this direction involves the use of multiple liquid phases. For example, rhodium complexes with water-soluble sulfonated ligands are used to catalyze alkene hydroformyla-tion, and the aqueous-phase catalyst and the organic products are easily separated as insoluble liquid phases. 

Wetland remediation involves a combination of interactions including microbial adsorption of metals, metal bioaccumulation, bacterial oxidation of metals, and sulfate reduction (Fennessy Mitsch, 1989 Kleinmann Hedin, 1989). Sulfate reduction produces sulfides which in turn precipitate metals and reduce aqueous metal concentrations. The high organic matter content in wetland sediments provides the ideal environment for sulfate-reducing populations and for the precipitation of metal complexes. Some metal precipitation may also occur in response to the formation of carbonate minerals (Kleinmann Hedin, 1989). In addition to the aforementioned microbial activities, plants, including cattails, grasses, and mosses, serve as biofilters for metals (Brierley, Brierley Davidson, 1989). 

The effects of adding various metal ions and metal complexes on the rate of a model oxidation reaction have been studied in some detail The model reaction chosen—the oxidation of ethanethiol in aqueous alkaline solution in the presence of metal-containing catalysts—involves the transfer of an electron from the thiol anion to the metal The catalytic activity of additives depends upon the solubility of the particular metal complex and varies according to the nature of the ligand attached to the metal ion. In conjunction with different metals, the same ligand can act either as a catalyst or as an inhibitor. The results are discussed in the light of proposed reaction mechanisms. 

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