Metal ion formation

In common with other hydroxy organic acids, tartaric acid complexes many metal ions. Formation constants for tartaric acid chelates with various metal ions are as follows Ca, 2.9 Cu, 3.2 Mg, 1.4 and Zn, 2.7 (68). In aqueous solution, tartaric acid can be mildly corrosive toward carbon steels, but under normal conditions it is noncorrosive to stainless steels (Table 9) (27). 

Chelates Heavy metals or bases Chelating agents such as by extraction of the metal ions Formation of stable metal chelates ... 

Selection-coupled analysis/phase segregation. One strategy for simplifying the analytical challenge is to use phase segregation. Three subclasses are possible. In the first of these, a phase transition is part of the selection process. This includes not only the familiar crystallization-induced enantiomeric enrichment discussed above but also the experiments (primarily employed in experiments directed toward the production of novel materials) such as those described by Lehn and coworkers in 2005. In this study, an acylhydrazone library was created from guanosine hydrazide and a mixture of aldehydes (Fig. 1.22) in the presence of metal ions, formation of G-quartet structures led to the production of a gel. 

Figure 1. Proposed mechanistic model for the Wittig reaction of nonstabilized and semistabilized ylides with aldehydes in the presence of soluble metal ions. Formation of the metallated betaines represents the step that determines the stereocontrol of the reaction.

So pronounced is the chelating tendency of the diketonate anion that even alkali metal complexes may be isolated, as illustrated by RbiKCFjCOCHCOCFjljNa], in which sodium is surrounded by a trigonal prismatic array of donor oxygen atoms. For complexes derived from dibenzoylmetbane, stabilities in dioxane-water are in the order Li > Na > K > Cs. For divalent metal ions formation constants increase in the order Ba > Sr > Ca > Mg > Cd > Mn > Pb > Zn > Co, Ni, Fe > Cu, and for higher valent metal ions the first formation constants for chelates are in the order Fe + > Ga " " > Th" > In " " > Sc " " > Y " " > Sm " > Nd " > More recently, such stu-... 

All mass spectra were obtained with a Fourier transform ion cyclotron resonance mass spectrometer (FTMS). The theory and applications of FTMS spectrometry are well-established and will not be discussed here. In our apparatus the sample was located at one of the trap plates of the cell, inside a superconducting magnet. Two pulsed lasers were used, one for tire PFPE desorption and another for metal ion formation. Typically, 2 to 4 mj/pulse of 248 nm or 193-nm light (20 ns fwhm) from an excimer laser was softly focused to an elliptical spot with a 2-mm long axis for desorption. To create the metal ions, a 0.3-mJ pulse of 532-nm light (10 ns fwhm) from the doubled output of a Nd YAG was tightly focused. The metal substrates were prepared from foils of various metals (typically 0.010 in. tiiick). Surface preparation was not critical because the experiment was not sensitive to PFPE/metal surface interactions since the thickness of the polymer films was on the order of 1 pm. 

In the presence of excess NH3, common to some synthetic fertilizer solutions, the corrosion rate in ammonium nitrate at room temperature may reach the very high value of 50mm/y (2ipy). The complex formed in this case has the structure [Fe(NH3)6](N03)2 [31], Since coupling mild steel to an equal area of platinum has no effect on the rate, the reaction is apparently anodicaUy controlled. Metallurgical structure affects the rate, a cold-worked mild steel reacting much more rapidly than one quenched from elevated temperature. This indicates that the reaction is not diffusion-controlled, but depends instead on the rate of metal-ion formation at the anode and perhaps also to some extent on the rate of depolarization at the cathode. 

Because of ammine formation, when ammonia solution is added slowly to a metal ion in solution, the hydroxide may first be precipitated and then redissolve when excess ammonia solution is added this is due to the formation of a complex ammine ion, for example with copper(II) and nickel(II) salts in aqueous solution. 

Unfortunately, addition of copper(II)nitrate to a solution of 4.42 in water did not result in the formation of a significant amount of complex, judging from the unchanged UV-vis absorption spectrum. Also after addition of Yb(OTf)3 or Eu(N03)3 no indications for coordination were observed. Apparently, formation of a six-membered chelate ring containing an amine and a ketone functionality is not feasible for these metal ions. Note that 4.13 features a similar arrangement and in aqueous solutions, likewise, does not coordinate significantly to all the Lewis acids that have been... 

Further evidence for an increased efficiency of complexation in the presence of micellar aggregates with bivalent metal counterions is presented in Table 5.4. The apparent rate constants of the reaction of 5.1c with 5.2 in the presence of micelles of Co(DS)2, Ni(DS)2, Cu(DS)2 and Zn(DS)2 are compared to the rate constants for the corresponding bivalent metal ion - dienophile complexes in the absence of micelles. The latter data are not dependent on the efficiency of the formation of the catalyst - dienophile complex whereas possible incomplete binding will certainly be reflected in the former. The good correlations between 1 and and the absence of a correlation between and... 

Synthesis by high-dilution techniques requires slow admixture of reagents ( 8-24 hrs) or very large volumes of solvents 100 1/mmol). Fast reactions can also be carried out in suitable flow cells (J.L. Dye, 1973). High dilution conditions have been used in the dilactam formation from l,8-diamino-3,6-dioxaoctane and 3,6-dioxaoctanedioyl dichloride in benzene. The amide groups were reduced with lithium aluminum hydride, and a second cyclization with the same dichloride was then carried out. The new bicyclic compound was reduced with diborane. This ligand envelops metal ions completely and is therefore called a cryptand (B. Dietrich, 1969). 

The formation constants of EDTA complexes are gathered in Table 11.34. Based on their stability, the EDTA complexes of the most common metal ions may be roughly divided into three groups ... 

The formation constant for a metal—ligand complex in which only one ligand is added to the metal ion or to a metal—ligand complex Ki). 

Finding the End Point with a Visual Indicator Most indicators for complexation titrations are organic dyes that form stable complexes with metal ions. These dyes are known as metallochromic indicators. To function as an indicator for an EDTA titration, the metal-indicator complex must possess a color different from that of the uncomplexed indicator. Furthermore, the formation constant for the metal-indicator complex must be less favorable than that for the metal-EDTA complex. 

The shift in the voltammogram for a metal ion in the presence of a ligand may be used to determine both the metal-ligand complex s stoichiometry and its formation constant. To derive a relationship between the relevant variables we begin with two equations the Nernst equation for the reduction of O... 

Certain compounds, known as chelating agents (qv), react synergisticaHy with many antioxidants. It is beheved that these compounds improve the functional abiUties of antioxidants by complexing the metal ions that often initiate free-radical formation. Citric acid and ethylenediaminetetraacetic acid [60-00-4] (EDTA), C2QH2gN20g, are the most common chelating agents used (22). 

---