In 1993, Periana et al. reported a synthesis of methyl bisulfate from methane using a mercury catalyst at 180 °C. Mercuric bisulfate activates methane electrophilically to form a methyl-complex, which then reacts with sulfuric acid to produce methyl bisulfate. The resulting mercury complex Hg(OSO) is re-oxidized by sulfuric acid to regenerate the catalyst and restart the catalytic cycle (). 
This method of functionalizing methane preceded the 1998 discovery by the same group of the so-called Catalytica system, the most active cycle to date in terms of turnover rate, yields, and selectivity. Performing the reaction in sulfuric acid at 220 °C means that the catalyst must be able to withstand these harsh conditions. A platinum-bipyrimidine complex serves as the catalyst. The mechanism for this system is similar to the one described above, where methane is first activated electrophilically to form a methyl-platinum intermediate. The Pt(II) complex is then oxidized to Pt(IV) as two sulfuric acid groups are added to the complex. The reductive elimination of methyl bisulfate transforms the Pt(IV) species back to Pt(II) to regenerate the catalyst ().
In a hypothetical combined process, the Catalytica system could be used in a net conversion of methane to methanol. The methyl bisulfate produced in the cycle could be converted to methanol by hydrolysis, and the sulfur dioxide generated could be converted back to sulfuric acid.