Platinum(IV) Chloride - Formation and Reactions

Formation and Reactions

PtCl4 is mainly encountered in the handling of chloroplatinic acid, obtained by dissolving of Pt metal in aqua regia. Heating H2PtCl6 gives PtCl4:

H2PtCl6 → PtCl4 + 2 HCl

If excess acids are removed, PtCl4 crystallizes from aqueous solutions in large red crystals of pentahydrate PtCl4·5(H2O), which can be dehydrated by heating to about 300 °C in a current of dry chlorine. The pentahydrate is stable and is used as the commercial form of PtCl4.

Treatment of PtCl4 with aqueous base gives the 2− ion. With methyl Grignard reagents followed by partial hydrolysis, PtCl4 converts to the cuboidal cluster 4. Upon heating PtCl4 evolves chlorine to give PtCl2:

PtCl4 → PtCl2 + Cl2

The heavier halides, PtBr4 and PtI4, are also known.

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