Aluminium complexes, 276 - reactions

To the cold acid chloride add 175 ml. of pure carbon disulphide, cool in ice, add 30 g, of powdered anhydrous aluminium chloride in one lot, and immediately attach a reflux condenser. When the evolution of hydrogen chloride ceases (about 5 minutes), slowly warm the mixture to the boiling point on a water bath. Reflux for 10 minutes with frequent shaking the reaction is then complete. Cool the reaction mixture to 0°, and decompose the aluminium complex by the cautious addition, with shaking, of 100 g. of crushed ice. Then add 25 ml. of concentrated hydrochloric acid, transfer to a 2 htre round-bottomed flask and steam distil, preferably in the apparatus, depicted in Fig. II, 41, 3 since the a-tetralone is only moderately volatile in steam. The carbon disulphide passes over first, then there is a definite break in the distillation, after whieh the a-tetralone distils completely in about 2 htres of distillate. 

The common ion effect (Chapter 3) is a further important factor affecting solubilities. Addition of A or B to the above system (equation (5.28)) will shift the equilibrium to the left and reduce the solubility of AB. In practice, this situation would arise when an excess of a precipitating reagent has been added to an analyte solution. Such an excess leads to the possibility of complexation reactions occurring which will tend to increase the solubility of AB. For example, when aluminium or zinc is precipitated by hydroxyl ions, the following reactions with excess reagent can occur... 

The review of Martynova (18) covers solubilities of a variety of salts and oxides up to 10 kbar and 700 C and also available steam-water distribution coefficients. That of Lietzke (19) reviews measurements of standard electrode potentials and ionic activity coefficients using Harned cells up to 175-200 C. The review of Mesmer, Sweeton, Hitch and Baes (20) covers a range of protolytic dissociation reactions up to 300°C at SVP. Apart from the work on Fe304 solubility by Sweeton and Baes (23), the only references to hydrolysis and complexing reactions by transition metals above 100 C were to aluminium hydrolysis (20) and nickel hydrolysis (24) both to 150 C. Nikolaeva (24) was one of several at the conference who discussed the problems arising when hydrolysis and complexing occur simultaneously. There appear to be no experimental studies of solution phase redox equilibria above 100°C. 

Techn. Univ. Leuna-Merseburg 29 432—443 Love, P. (1998) Minerals - are they just cosmetic Indust. Min. August 41-43 Lovgren, L. (1991) Complexation reactions of phthalic acid and aluminium(III) with the surface of goethite. Geochim. Cosmochim. Acta 55 3639-3645... 

Chiral aluminium complexes have been used as catalysts for inverse electron-demand 1,3-dipolar cycloadditions of alkenes with nitrones, and the first contribution to this field was pubhshed in 1999 (344). The chiral AlMe-BEMOL (BINOL = 2,2 -bis(diphenylphosphino)-l,l -binaphthyl) complexes 235 were excellent catalysts for the reaction between nitrone 225a and vinyl ethers 232 (Scheme 12.68). The diastereo- and enantioselectivities are highly dependent on the chiral ligand. An exo/endo ratio of 73 27 was observed, and the exo-product was... 

The enantioselective inverse electron-demand 1,3-dipolar cycloadditions of nitrones with alkenes described so far are catalyzed by metal complexes that favor a monodentate coordination of the nitrone, such as boron and aluminium complexes. However, the glyoxylate-derived nitrone 256 favors abidentate coordination to the catalyst, and this nitrone is an interesting substrate, since the products that are obtained from the reaction with alkenes are masked ot-amino acids (Scheme 12.81). 

Complexations with metal complexing cations such as aluminium are included by writing the complexations reaction of the metal with a diprotic complexation site, e.g. 

Lovgren, L., Hedlund, T., Oilman, L.-O. and Sjoberg, S. (1987) Equilibrium approaches to natural water systems - 6. Acid-base properties of a concentrated bog-water and its complexation reactions with aluminium(III). Water Res., 21(11), 1401-1407. 

The same three spectrophotometric reagents were compared for their abilities to differentiate mono- and polynuclear hydroxy-aluminium complexes in solutions typical of those used in phytotoxicity studies (Parker et al., 1988b). Methods based upon each of the three reagents yielded estimates of the mononuclear aluminium fraction of adequate precision for most purposes. Studies using ferron demonstrated its utility for characterising the non-mononuclear aluminium fraction using kinetic analyses. The ferron spectrophotometric procedure was preferred for its simplicity, level of precision and moderate rate of reaction with aluminium. 

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