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Molybdenum Oxychlorides

Several Molybdenum Oxychlorides have been described. The compounds Mo2O3Cl2 and Mo3O3Cl7 have been stated to be formed by the reduction of the oxychloride MoOCl4.

The compound Mo2O3Cl5 was stated by Blomstrand to be formed as reddish-brown, fusible crystals by condensation of the brown vapours which are produced when chlorine is passed over heated molybdenum sesquioxide, Mo2O3.

The oxychloride MoO2Cl2 is obtained when chlorides of molybdenum are heated in the air, and, among other compounds, when the dioxide, or a mixture of the trioxide with carbon, is heated in chlorine, or when molybdenum trioxide and phosphorus trichloride are heated together; it is not formed, however, when a mixture of common salt, sulphuric acid, and molybdenum trioxide is heated. A pale yellow amorphous substance, soluble in water and alcohol, it is easily sublimed, and is reduced on heating in hydrogen or carbon monoxide to the dioxide.

The compound Mo3O5Cl8 is stated to be a stable red crystalline substance which is produced on heating the compound Mo2O3Cl6; the latter is a violet crystalline deliquescent body, soluble in water, produced by reduction in hydrogen of the oxychloride MoOCl4. It sublimes on heating; when heated in the air it is oxidised to the oxychloride MoO2Cl2 and chlorine; its aqueous solution is unstable.

The oxychloride MoOCl4 is formed on heating in chlorine a mixture of molybdenum pentachloride and the compound MoO2Cl2:

2MoCl5 + 2MoO2Cl2 + Cl2 = 4MoOCl4;

or by using instead appropriate quantities of the metal and the dioxide. The substance is considered by Nordenskjold to be a mixture in varying proportions of the pentachloride with the oxychloride MoO2Cl2. The crystals obtained, on purification by sublimation, have a dark green colour and metallic lustre. They readily fuse and vaporise, and are affected by sunlight. The aqueous solution is unstable; on heating alone, the compound Mo2O3Cl6 is formed; while in hydrogen it gives the oxychlorides Mo3O3Cl7 and MoO2Cl2, molybdenum dichloride and molybdenum.

The following compounds have also been prepared: MoOCl3.2NH4Cl, MoOCl3.2KCl.2H2O, MoOCl3.2RbCl, MoOCl3.2CsCl, together with similar compounds with certain organic bases.

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