Nickel-copper boride

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). 

Three new methods for the conversion of alkynes to (Z)-alkenes were reported, although Lindlar semi-hydrogenation still remains as the most convenient method. Copper (I) hydride reagent could reduce alkynes to (Z)-alkenes as shown in Scheme 3 [12]. Yoon employed nickel boride prepared on borohy-dride exchange resin for selective hydrogenation of alkynes to (Z)-alkenes (Scheme 4) [13]. 

Hydroborate Reduction. Lithium or sodium tetrahydroborate and diborane can be used for reduction of metal ions, especially light transition metal ions, to produce colloidal metals. For example, colloidal copper protected by polymer was prepared by reduction of copper(II) sulfate by a large excess of sodium tetrahydroborate in the presence of PVP or other polymers (12). A similar procedure for nickel(III) chloride produced nickel boride, not zero-valence nickel metal particles. 

Nickel, either as a Raney catalyst or in the form of nickel boride, is also effective in the reduction of the C=0 bond. An increase in the catalytic activity can be brought about by metal promoters (chromium and molybdenum). Copper chromite may also be used. 

Nitta et al. compared the selectivity of copper, cobalt, and nickel borides (Cu-B, Co-B, and Ni-B) as well as Raney Ni and Ni-B modified with copper(II) chloride, in the partial hydrogenation of acetylenic compounds.82 The selectivity at 30% conversion... 

Hydrogenation Copper chromite (Lazier catalyst). Copper chromium oxide (Adkins catalyst). Lindlar catalyst (see also Lithium ethoxyacetylide, Malealdehyde, Nickel boride). Nickel catalysts. Palladium catalysts. Palladium hydroxide on carbon. Perchloric acid (promoter). Platinum catalysts. Raney catalysts, Rhenium catalysts. Rhodium catalysts. Stannous chloride. Tributylborane. Trifluoroicetic acid, Tris (triphenylphosphine)chlororhodium. 

Although palladium occupies the dominant position in semi-hydrogenation catalysts, it is by no means the only metal suitable for formulation into a viable catalyst. Mention has already been made of the nickel boride alternatives, with or without copper promotion, for example. Other examples include the skeletal catalyst Raney nickel [69], alumina-supported nickel [70], and aluminum phosphate-supported nickel [71] (Eqs 21 and 22) ... 

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