 | |
| Names | |
|---|---|
| IUPAC name Platinum(IV) oxide | |
| Other names platinum dioxide, platinic oxide | |
| Identifiers | |
3D model (JSmol) | |
| ChemSpider |
|
| ECHA InfoCard | 100.013.840 |
| UNII | |
| |
| |
| 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 inalcohol,acid,aqua regia soluble incaustic potash solution |
| −37.70·10−6 cm3/mol | |
| Hazards | |
| GHS labelling: | |
 | |
| Danger | |
| H271 | |
Except where otherwise noted, data are given for materials in theirstandard state (at 25 °C [77 °F], 100 kPa). | |
Adams' catalyst, also known asplatinum dioxide, is usually represented asplatinum(IV)oxidehydrate, PtO2•H2O. It is a catalyst forhydrogenation andhydrogenolysis inorganic synthesis.[1] 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 toplatinum black, which is responsible for reactions.
Adams' catalyst is prepared fromchloroplatinic acid H2PtCl6 orammonium chloroplatinate, (NH4)2PtCl6, by fusion withsodium nitrate. The first published preparation was reported by V. Voorhees andRoger Adams.[2] The procedure involves first preparing a platinum nitrate which is then heated to expel nitrogen oxides.[3]
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 usingaqua regia followed byammonia.
Adams' catalyst is used for many applications. It has shown to be valuable forhydrogenation,hydrogenolysis,dehydrogenation, andoxidation reactions. During the reaction, platinum metal (platinum black) is formed which has been cited to be the active catalyst.[4][5] 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 orethers (the latter product forming in the presence of alcohols and acids)[6] and thereduction of nitro compounds to amines.[7] However, reductions ofalkenes can be performed with Adams' catalyst in the presence of nitro groups without reducing the nitro group.[8] 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.
Before development of Adams' catalyst, organic reductions were carried out using colloidal platinum or platinum black. The colloidal catalysts were more active but posed difficulties in isolating reaction products. This led to more widespread use of platinum black. In Adams' own words:
"...Several of the problems I assigned my students involved catalytic reduction. For this purpose we were using as a catalystplatinum black made by the generally accepted best method known at the time. The students had much trouble with the catalyst they obtained in that frequently it proved to be inactive even though prepared by the same detailed procedure which resulted occasionally in an active product. I therefore initiated a research to find conditions for preparing this catalyst with uniform activity."[4]
Little precaution is necessary with the oxide but, after exposure to H2, the resulting platinum black can bepyrophoric. Therefore, it should not be allowed to dry and all exposure to oxygen should be minimized.
