Borides, hydrogen reactions

Adiponitrile undergoes the typical nitrile reactions, eg, hydrolysis to adipamide and adipic acid and alcoholysis to substituted amides and esters. The most important industrial reaction is the catalytic hydrogenation to hexamethylenediarnine. A variety of catalysts are used for this reduction including cobalt—nickel (46), cobalt manganese (47), cobalt boride (48), copper cobalt (49), and iron oxide (50), and Raney nickel (51). An extensive review on the hydrogenation of nitriles has been recendy pubUshed (10). 

Hafnium Boride. Hafnium diboride [12007-23-7] HfB2, is a gray crystalline soHd. It is usually prepared by the reaction of hafnium oxide with carbon and either boron oxide or boron carbide, but it can also be prepared from mixtures of hafnium tetrachloride, boron trichloride, and hydrogen above 2000°C, or by direct synthesis from the elements. Hafnium diboride is attacked by hydrofluoric acid but is resistant to nearly all other reagents at room temperature. Hafnium dodecaboride [32342-52-2] has been prepared by direct synthesis from the elements (56). 

Bonding is used extensively on steel. The reaction occurs with a high hydrogen dilution of the BCI3 to prevent substrate attack. An iron boride is formed. 1 1 Not all metals, however, are suitable to bonding. For instance, the bonding of titanium by CVD in a chloride-based system is more difficult since the titanium substrate is highly susceptible to HCl attack and the rate of diffusion is low. 

Borides of Group IVa. UB2, ZrB2, and HfB2 are readily deposited by the hydrogen reduction of the metal halide, usually the chloride. Atypical reaction is as follows ... 

Moreover, stable liquid systems made up of nanoparticles coated with a surfactant monolayer and dispersed in an apolar medium could be employed to catalyze reactions involving both apolar substrates (solubilized in the bulk solvent) and polar and amphiphilic substrates (preferentially encapsulated within the reversed micelles or located at the surfactant palisade layer) or could be used as antiwear additives for lubricants. For example, monodisperse nickel boride catalysts were prepared in water/CTAB/hexanol microemulsions and used directly as the catalysts of styrene hydrogenation [215]. 

As we shall see later, borides (as well as oxides, nitrides, carbides, etc.) react with water to produce a hydrogen compound of the nonmetal. Thus, the reaction of magnesium boride with water might be expected to produce BH3, borane, but instead the product is B2ff6, diborane (m.p. -165.5 °C, b.p. -92.5 °C). This interesting covalent hydride has the structure... 

Sodium hydrogen telluride reacts with epoxides, in accordance with an S 2 displacement, giving rise to telluro-alcohols. These products are useful intermediates since they are easily converted into the corresponding alcohols and ketones by treatment with nickel boride followed by oxidation (reaction (a)) or to alkenes via the corresponding tosylates (reaction b)). ... 

This reaction, which generates nickel boride, is exothermic and evolves hydrogen. Frothing is prevented by keeping the reaction mixture at 0-5°C during addition of the sodium borohydride. 

O-p-tolylsulfonyl-a-D-mannoside (39) in 37% yield. Treatment of (39) with sodium iodide in acetone gave the 6-iodo derivative (40), which underwent reduction with hydrogen in the presence of a nickel boride" catalyst" to give methyl 4-0-benzoyl-2,3-0 carbonyl-6-deoxy-o>-D-manno-side (41) in 95% yield. Reaction of (41) with hydrogen bromide in acetic acid effected replacement of the methoxyl group at C-l, affording crystalline... 

Unsaturated aldehydes.4 A nickel boride catalyst similar to P-2 nickel boride is obtained by reaction of NiCl2 and excess NaBH4 in C2H5OH. It effects selective hydrogenation of a,P-alkynal acetals to the (Z)-a,p-alkenal acetals. 

Borides Carbon boride, CB6. and silicon borides SiB3 and SiB6 are hard, crystalline solids, produced in ihe electric furnace magnesium boride, Mgi B2, brown solid, by reaction of boron oxide and magnesium powder ignited, forms boron hydrides with HC1 calcium boride, Ca3 B2, forms boron hydrides and hydrogen gas with IIC1. 

Benzaldehyde has been hydrogenated on Pd/C(l), Raney nickel and nickel boride (2) catalysts. Baltzly (Ref. 1) measured the rate of hydrogen pressure decrease as a function of time in a batch reactor. He found that the rate of reaction was zero order for both reactants at hydrogen pressures above 3 atm. and benzaldehyde concentrations above 1.0 gmol/1. The rate data was obtained at 22°C in various solvents. No measurements of the products and the benzaldehyde were reported. For the 3% Pd/C catalyst, the rate of reaction was 1.6 x 10 2 gmol/g.min, independent of the type of solvent. 

In contrast to Lindlar catalyst we have found that the hydrogenation of an alkyne over ethylenediamine-poisoned "P-2" nickel boride or quinoline-poisoned palladium-on-barium sulfate always gives a minor amount of the saturated hydrocarbon in addition to the olefin. The ratio of saturated hydrocarbon to olefin (about 0.01) also is nearly constant throughout the hydrogenation until the alkyne is consumed, and then it increases. Further reaction of the alkene on the catalyst surface before desorption would explain these results. 

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