Metal hydrides, properties

Hauback BC (2008) Metal hydrides properties and applications of alanates. Encyclopedia of Materials Sci Tech 1-5... 

Alkali Metal Hydrides. Physical properties of the alkaU metal hydrides are given in Table 1. 

Table 1. Physical Properties of Alkali Metal Hydrides...

Potassium, Pubidium, and Cesium idjdrides. Although all the other alkah metal hydrides have been synthesized and some of the properties measured, only potassium hydride [7693-26-7] is commercially available. KH is manufactured in small amounts and sold as a mineral oil dispersion. It is a stronger base than NaH and is used to make the strong reducing agent KBH(C2H )2 and the super bases RNHK and ROK (6). 

Trunsition-MetnlHydrides, Tiansition-metal hydiides, ie, inteistitial metal hydrides, have metalhc properties, conduct electricity, and ate less dense than the parent metal. Metal valence electrons are involved in both the hydrogen and metal bonds. Compositions can vary within limits and stoichiometry may not always be a simple numerical proportion. These hydrides are much harder and more brittie than the parent metal, and most have catalytic activity. 

Tetrahydroborates. The tetrahydroboranes constitute the most commercially important group of boron hydride compounds. Tetrahydroborates of most of the metals have been characterized and their preparations have been reviewed (46). The important commercial tetrahydroborates are those of the alkah metals. Some properties are given ia Table 4. 

Greater selectivity in purification can often be achieved by making use of differences in chemical properties between the substance to be purified and the contaminants. Unwanted metal ions may be removed by precipitation in the presence of a collector (see p. 54). Sodium borohydride and other metal hydrides transform organic peroxides and carbonyl-containing impurities such as aldehydes and ketones in alcohols and ethers. Many classes of organic chemicals can be purified by conversion into suitable derivatives, followed by regeneration. This chapter describes relevant procedures. 

There are few systematic guidelines which can be used to predict the properties of AB2 metal hydride electrodes. Alloy formulation is primarily an empirical process where the composition is designed to provide a bulk hydride-forming phase (or phases) which form, in situ, a corrosion— resistance surface of semipassivating oxide (hydroxide) layers. Lattice expansion is usually reduced relative to the ABS hydrides because of a lower VH. Pressure-composition isotherms of complex AB2 electrode materials indicate nonideal behaviour. 

These compounds are generally believed to have square pyramidal structures (X-ray, PPr3) [157d] and have typical spectroscopic properties of transition-metal hydrides (IrHCl2(PBu2Me)2 i/(Ir—H) 1998 cm-1). 

Presumably, the stereoselectivity in these cases is the result of coordination of iridium by the functional group. The crucial property required for a catalyst to be stereodirective is that it be able to coordinate with both the directive group and the double bond and still accommodate the metal hydride bonds necessary for hydrogenation. In the iridium catalyst illustrated above, the cyclooctadiene ligand (COD) in the catalysts is released by hydrogenation, permitting coordination of the reactant and reaction with hydrogen. 

Bronger, W. and G. Auffermann, New ternary alkali-metal-transition-metal hydrides synthesized at high pressures Characterization and properties, Chem. Mater., 10, 2723,1998. 

By far the most important redox reaction relative to chemical stability is the reaction between an oxidizable material and oxygen from air. The particle size and any droplets have a large effect on the combustion properties. Some substances react so rapidly in air that ignition occurs spontaneously. These so called pyrophoric compounds (white phosphorus, alkali metals, metal hydrides, some metal catalysts, and fully alkylated metals and nonmetals) must be stored in the absence of air. 

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