Direct
catalytic functionalization of methane, a “dream
reaction”, is typically characterized by poorly active catalysts
and low product selectivity. Selectivity is particularly high for
the “Periana system”, in which methane is oxidized to
methyl bisulfate in sulfuric acid/oleum using a η2-(2,2′-bipyrimidyl)dichloroplatinum(II) ((bpym)PtCl2, 1) catalyst. Recently it was shown that well-chosen
reaction conditions result in not only high selectivity but also remarkably
high activity, previously considered to be the prohibiting factor
regarding commercialization. The high activity apparently contradicts
the original report. Detailed studies of the dependence of activity
and selectivity on the catalyst concentration resolve this contradiction
and reveal solubility, transformation of catalyst precursors, speciation,
and solubility of methane as crucial factors for the observed reaction
rates. Additionally, the selectivity pattern clearly discloses the
consecutive nature of the reaction network.