Heteropoly metallates

In 1987 we published the first review on the magnetism of heteropoly-metallic systems (3). This article was largely devoted to the mechanism of the interaction in heterobinuclear complexes. The field of heteropoly-metallic compounds was covered up to the first attempts to obtain molecular-based magnets. The very last sentence of this article was One may anticipate that in a few years another review will be necessary, and that its main emphasis will be on systems of higher nuclearity and extended systems with subtle spin orders. In the present case, our prediction was quite correct, which is not so frequent in science. The field of heterobimetallic systems has developed tremendously since 1987, particularly in relation to the synthesis of molecular-based magnets. It is now timely to write a second review concerning this topic. 

Protonic initiation is also the end result of a large number of other initiating systems. Strong acids are generated in situ by a variety of different chemistries (6). These include initiation by carbenium ions, eg, trityl or diazonium salts (151) by an electric current in the presence of a quartenary ammonium salt (152) by halonium, triaryl sulfonium, and triaryl selenonium salts with uv irradiation (153—155) by mercuric perchlorate, nitrosyl hexafluorophosphate, or nitryl hexafluorophosphate (156) and by interaction of free radicals with certain metal salts (157). Reports of "new" initiating systems are often the result of such secondary reactions. Other reports suggest standard polymerization processes with perhaps novel anions. These latter include (Tf)4Al (158) heteropoly acids, eg, tungstophosphate anion (159,160) transition-metal-based systems, eg, Pt (161) or rare earths (162) and numerous systems based on tri flic acid (158,163—166). Coordination polymerization of THF may be in a different class (167). 

These appHcations are mosdy examples of homogeneous catalysis. Coordination catalysts that are attached to polymers via phosphine, siloxy, or other side chains have also shown promise. The catalytic specificity is often modified by such immobilization. Metal enzymes are, from this point of view, anchored coordination catalysts immobilized by the protein chains. Even multistep syntheses are possible using alternating catalysts along polymer chains. Other polynuclear coordination species, such as the homopoly and heteropoly ions, also have appHcations in reaction catalysis. 

In 1826 J. J. Berzelius found that acidification of solutions containing both molybdate and phosphate produced a yellow crystalline precipitate. This was the first example of a heteropolyanion and it actually contains the phos-phomolybdate ion, [PMoi204o] , which can be used in the quantitative estimation of phosphate. Since its discovery a host of other heteropolyanions have been prepared, mostly with molybdenum and tungsten but with more than 50 different heteroatoms, which include many non-metals and most transition metals — often in more than one oxidation state. Unless the heteroatom contributes to the colour, the heteropoly-molybdates and -tungstates are generally of varying shades of yellow. The free acids and the salts of small cations are extremely soluble in water but the salts of large cations such as Cs, Ba" and Pb" are usually insoluble. The solid salts are noticeably more stable thermally than are the salts of isopolyanions. Heteropoly compounds have been applied extensively as catalysts in the petrochemicals industry, as precipitants for numerous dyes with which they form lakes and, in the case of the Mo compounds, as flame retardants. 

Ethyl acetate is an oxygenated solvent widely used in the inks, pharmaceuticals and fragrance sectors. The current global capacity for ethyl acetate is 1.2 million tonnes per annum. BP Chemicals is the world s largest producer of ethyl acetate. Conventional methods for the production of ethyl acetate are either via the liquid phase esterification of acetic acid and ethanol or by the coupling of acetaldehyde also known as the Tischenko reaction. Both of these processes require environmentally unfriendly catalysts (e.g. p-toluenesulphonic acid for the esterification and metal chlorides and strong bases for the Tischenko route). In 1997 BP Chemicals disclosed a new route to produce ethyl acetate directly from the reaction of ethylene with acetic acid using supported heteropoly acids... 

Acidity, 27 284, 285 catalytic performance, 30 121 crystalline titanium silicates, 41 319-320 estimating, 37 166 heteropoly compounds, 41 139-150 ion exchange and, zeolites, 31 5-6 sulfate-supported metal oxides, 37 186-187 surface, monolayer dispersion, 37 34-35 tin-antimony oxide, 30 114-115, 125-1256 Acids, see also specific compounds adsorption of, on oxide surfaces, 25 243-245... 

Cu in solid solution, 31 259-260 Scanning tunneling microscopy chemisorbed hydrocarbons on metals, 41 30 heteropoly compounds, 41 137 molecular precursors for tailored metal catalysts, 38 303-305... 

Moffat, J. B. Metal-Oxygen Clusters The Surface and Catalytic Properties of Heteropoly Oxometalates vol. 9 Kluwer Academic/Plenum Publishers New York, 2001. 

Melting a mixture of germanium dioxide and metal oxides produces ortho-and metagermanates of the corresponding metals. Aqueous solutions of ger-manate react with molyhdic and tungstic acids forming heteropoly acids of varying compositions. 

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