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Platinum dioxide

Adams's catalyst
Adams's catalyst.svg
Names
IUPAC name
Platinum(IV) oxide
Other names
platinum dioxide, platinic oxide
Identifiers
3D model (Jmol)
ChemSpider
ECHA InfoCard 100.013.840
Properties
PtO2
Molar mass 227.08 g/mol
Appearance black solid
Density 10.2 g/cm³
Melting point 450 °C (842 °F; 723 K)
insoluble
Solubility insoluble in alcohol, acid, aqua regia
soluble in caustic potash solution
−37.70·10−6 cm3/mol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
YesY  (what is YesYN ?)
Infobox references

Adams's catalyst, also known as platinum dioxide, is usually represented as platinum(IV) oxide hydrate, PtO2•H2O. It is a catalyst for hydrogenation and hydrogenolysis in organic synthesis. This dark brown powder is commercially available. The oxide itself is not an active catalyst, but it becomes active after exposure to hydrogen whereupon it converts to platinum black, which is responsible for reactions.

Adams's catalyst is prepared from chloroplatinic acid H2PtCl6 or ammonium chloroplatinate, (NH4)2PtCl6, by fusion with sodium nitrate. The first published preparation was reported by V. Voorhees and Roger Adams. The procedure involves first preparing a platinum nitrate which is then heated to expel nitrogen oxides.

The resulting brown cake is washed with water to free it from nitrates. The catalyst can either be used as is or dried and stored in a desiccator for later use. Platinum can be recovered from spent catalyst by conversion to ammonium chloroplatinate using aqua regia followed by ammonia.

Adams's catalyst is used for many applications. It has shown to be valuable for hydrogenation, hydrogenolysis, dehydrogenation, and oxidation reactions. During the reaction, platinum metal (platinum black) is formed which has been cited to be the active catalyst. Hydrogenation occurs with syn stereochemistry when used on an alkyne resulting in a cis-alkene. Some of the most important transformations include the hydrogenation of ketones to alcohols or ethers (the latter product forming in the presence of alcohols and acids) and the reduction of nitro compounds to amines. However, reductions of alkenes can be performed with Adam's catalyst in the presence of nitro groups without reducing the nitro group. When reducing nitro compounds to amines, platinum catalysts are preferred over palladium catalysts to minimize hydrogenolysis. The catalyst is also used for the hydrogenolysis of phenyl phosphate esters, a reaction that does not occur with palladium catalysts. The pH of the solvent significantly affects the reaction course, and reactions of the catalyst are often enhanced by conducting the reduction in neat acetic acid, or solutions of acetic acid in other solvents.


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