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Chemical reaction between molecular hydrogen and another compound or element

Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to reduce or saturate organic compounds. Hydrogenation typically constitutes the addition of pairs of hydrogen atoms to a molecule, often an alkene. Catalysts are required for the reaction to be usable; non catalytic hydrogenation takes place only at very high temperatures. Hydrogenation reduces double and triple bonds in hydrocarbons.

Hydrogenation has three components, the unsaturated substrate, the hydrogen (or hydrogen source) and, invariably, a catalyst. The reduction reaction is carried out at different temperatures and pressures depending upon the substrate and the activity of the catalyst.

The same catalysts and conditions that are used for hydrogenation reactions can also lead to isomerization of the alkenes from cis to trans. This process is of great interest because hydrogenation technology generates most of the trans fat in foods. A reaction where bonds are broken while hydrogen is added is called hydrogenolysis, a reaction that may occur to carbon carbon and carbon heteroatom (oxygen, nitrogen or halogen) bonds. Some hydrogenations of polar bonds are accompanied by hydrogenolysis.

For hydrogenation, the obvious source of hydrogen is |H2 gas itself, which is typically available commercially within the storage medium of a pressurized cylinder. The hydrogenation process often uses greater than 1 atmosphere of |H2, usually conveyed from the cylinders and sometimes augmented by "booster pumps". Gaseous hydrogen is produced industrially from hydrocarbons by the process known as steam reforming. For many applications, hydrogen is transferred from donor molecules such as formic acid, isopropanol, and dihydroanthracene. These hydrogen donors undergo dehydrogenation to, respectively, carbon dioxide, acetone, and anthracene. These processes are called transfer hydrogenations.

With rare exceptions, |H2 is unreactive toward organic compounds in the absence of metal catalysts. The unsaturated substrate is chemisorbed onto the catalyst, with most sites covered by the substrate. In heterogeneous catalysts, hydrogen forms surface hydrides (M H) from which hydrogens can be transferred to the chemisorbed substrate. Platinum, palladium, rhodium, and ruthenium form highly active catalysts, which operate at lower temperatures and lower pressures of |H2. Non precious metal catalysts, especially those based on nickel (such as Raney nickel and Urushibara nickel) have also been developed as economical alternatives, but they are often slower or require higher temperatures. The trade off is activity (speed of reaction) vs. cost of the catalyst and cost of the apparatus required for use of high pressures. Notice that the Raney nickel catalysed hydrogenations require high pressures:

Catalysts are usually classified into two broad classes: homogeneous and heterogeneous. Homogeneous catalysts dissolve in the solvent that contains the unsaturated substrate. Heterogeneous catalysts are solids that are suspended in the same solvent with the substrate or are treated with gaseous substrate.

Some well known homogeneous catalysts are indicated below. These are coordination complexes that activate both the unsaturated substrate and the |H2. Most typically, these complexes contain platinum group metals, especially Rh and Ir. Homogeneous catalysts are also used in asymmetric synthesis by the hydrogenation of prochiral substrates. An early demonstration of this approach was the Rh catalyzed hydrogenation of enamides as precursors to the drug L DOPA. To achieve asymmetric reduction, these catalyst are made chiral by use of chiral diphosphine ligands. In principle asymmetric hydrogenation can be catalyzed by chiral heterogeneous catalysts, but this approach remains more of a curiosity than a useful technology.

Heterogeneous catalysts for hydrogenation are more common industrially. In industry, precious metal hydrogenation catalysts are deposited from solution as a fine powder on the support, which is a cheap, bulky, porous, usually granular material, such as activated carbon, alumina, calcium carbonate or barium sulfate. For example, platinum on carbon is produced by reduction of chloroplatinic acid in situ in carbon. Examples of these catalysts are 5% ruthenium on activated carbon, or 1% platinum on alumina. Base metal catalysts, such as Raney nickel, are typically much cheaper and do not need a support. Also, in the laboratory, unsupported (massive) precious metal catalysts such as platinum black are still used, despite the cost. As in homogeneous catalysts, the activity is adjusted through changes in the environment around the metal, i. e. the coordination sphere. Different faces of a crystalline heterogeneous catalyst display distinct activities, for example. This can be modified by mixing metals or using different preparation techniques. Similarly, heterogeneous catalysts are affected by their supports. In many cases, highly empirical modifications involve selective "poisons". Thus, a carefully chosen catalyst can be used to hydrogenate some functional groups without affecting others, such as the hydrogenation of alkenes without touching aromatic rings, or the selective hydrogenation of alkynes to alkenes using Lindlar's catalyst. For example, when the catalyst palladium is placed on barium sulfate and then treated with quinoline, the resulting catalyst reduces alkynes only as far as alkenes. The Lindlar catalyst has been applied to the conversion of phenylacetylene to styrene.

Transfer hydrogenation uses hydrogen donor molecules other than molecular |H2. These "sacrificial" hydrogen donors, which can also serve as solvents for the reaction, include hydrazine, formic acid, and alcohols such as isopropanol. In organic synthesis, transfer hydrogenation is useful for the asymmetric hydrogenation of polar unsaturated substrates, such as ketones, aldehydes and imines, by employing chiral catalysts.

Polar substrates such as nitriles can be hydrogenated electrochemically, using protic solvents and reducing equivalents as the source of hydrogen.

Catalytic hydrogenation has diverse industrial uses. Most frequently, industrial hydrogenation relies on heterogeneous catalysts.

In petrochemical processes, hydrogenation is used to convert alkenes and aromatics into saturated alkanes (paraffins) and cycloalkanes (naphthenes), which are less toxic and less reactive. Relevant to liquid fuels that are stored sometimes for long periods in air, saturated hydrocarbons exhibit superior storage properties. On the other hand, alkenes tend to form hydroperoxides, which can form gums that interfere with fuel handling equipment. For example, mineral turpentine is usually hydrogenated. Hydrocracking of heavy residues into diesel is another application. In isomerization and catalytic reforming processes, some hydrogen pressure is maintained to hydrogenolyze coke formed on the catalyst and prevent its accumulation.

Hydrogenation is a useful means for converting unsaturated compounds into saturated derivatives. Substrates include not only alkenes and alkynes, but also aldehydes, imines, and nitriles, which are converted into the corresponding saturated compounds, i. e. alcohols and amines. Thus, alkyl aldehydes, which can be synthesized with the oxo process from carbon monoxide and an alkene, can be converted to alcohols. E. g. 1 propanol is produced from propionaldehyde, produced from ethene and carbon monoxide. Xylitol, a polyol, is produced by hydrogenation of the sugar xylose, an aldehyde. Primary amines can be synthesized by hydrogenation of nitriles, while nitriles are readily synthesized from cyanide and a suitable electrophile. For example, isophorone diamine, a precursor to the polyurethane monomer isophorone diisocyanate, is produced from isophorone nitrile by a tandem nitrile hydrogenation/reductive amination by ammonia, wherein hydrogenation converts both the nitrile into an amine and the imine formed from the aldehyde and ammonia into another amine.

The earliest hydrogenation was that of the platinum catalyzed addition of hydrogen to oxygen in the Döbereiner's lamp, a device commercialized as early as 1823. The French chemist Paul Sabatier is considered the father of the hydrogenation process. In 1897, building on the earlier work of James Boyce, an American chemist working in the manufacture of soap products, he discovered that traces of nickel catalyzed the addition of hydrogen to molecules of gaseous hydrocarbons in what is now known as the Sabatier process. For this work, Sabatier shared the 1912 Nobel Prize in Chemistry. Wilhelm Normann was awarded a patent in Germany in 1902 and in Britain in 1903 for the hydrogenation of liquid oils, which was the beginning of what is now a worldwide industry. The commercially important Haber–Bosch process, first described in 1905, involves hydrogenation of nitrogen. In the Fischer–Tropsch process, reported in 1922 carbon monoxide, which is easily derived from coal, is hydrogenated to liquid fuels. In 1922, Voorhees and Adams described an apparatus for performing hydrogenation under pressures above one atmosphere. The Parr shaker, the first product to allow hydrogenation using elevated pressures and temperatures, was commercialized in 1926 based on Voorhees and Adams' research and remains in widespread use. In 1924 Murray Raney developed a finely powdered form of nickel, which is widely used to catalyze hydrogenation reactions such as conversion of nitriles to amines or the production of margarine.

In the 1930s, Calvin discovered that copper(II) complexes oxidized H2. The 1960s witnessed the development of well defined homogeneous catalysts using transition metal complexes, e. g., Wilkinson's catalyst (RhCl(PPh3)3). Soon thereafter cationic Rh and Ir were found to catalyze the hydrogenation of alkenes and carbonyls. In the 1970s, asymmetric hydrogenation was demonstrated in the synthesis of L DOPA, and the 1990s saw the invention of Noyori asymmetric hydrogenation. The development of homogeneous hydrogenation was influenced by work started in the 1930s and 1940s on the oxo process and Ziegler–Natta polymerization.

For most practical purposes, hydrogenation requires a metal catalyst. Hydrogenation can, however, proceed from some hydrogen donors without catalysts, illustrative hydrogen donors being diimide and aluminium isopropoxide, the latter illustrated by the Meerwein–Ponndorf–Verley reduction. Some metal free catalytic systems have been investigated in academic research. One such system for reduction of ketones consists of tert butanol and potassium tert butoxide and very high temperatures. The reaction depicted below describes the hydrogenation of benzophenone:

A chemical kinetics study found this reaction is first order in all three reactants suggesting a cyclic 6 membered transition state. Another system for metal free hydrogenation is based on the phosphine borane, compound 1, which has been called a frustrated Lewis pair. It reversibly accepts dihydrogen at relatively low temperatures to form the phosphonium borate 2 which can reduce simple hindered imines. The reduction of nitrobenzene to aniline has been reported to be catalysed by fullerene, its mono anion, atmospheric hydrogen and UV light.

The original and still a commonly practised form of hydrogenation in teaching laboratories, this process is usually effected by adding solid catalyst to a round bottom flask of dissolved reactant which has been evacuated using nitrogen or argon gas and sealing the mixture with a penetrable rubber seal. Hydrogen gas is then supplied from a H2 filled balloon. The resulting three phase mixture is agitated to promote mixing. Hydrogen uptake can be monitored, which can be useful for monitoring progress of a hydrogenation. This is achieved by either using a graduated tube containing a coloured liquid, usually aqueous copper sulfate or with gauges for each reaction vessel.

Since many hydrogenation reactions such as hydrogenolysis of protecting groups and the reduction of aromatic systems proceed extremely sluggishly at atmospheric temperature and pressure, pressurised systems are popular. In these cases, catalyst is added to a solution of reactant under an inert atmosphere in a pressure vessel. Hydrogen is added directly from a cylinder or built in laboratory hydrogen source, and the pressurized slurry is mechanically rocked to provide agitation, or a spinning basket is used.