Shilov system

An equivalent transformation is performed industrially by steam reforming methane to syngas then reducing the carbon monoxide to methanol.

Overall Transformation RH + H2O + [PtCl6]2− → ROH + 2H+ + PtCl2 + 4Cl− The initial and rate limiting step involving the electrophilic activation of RH2C-H by a PtII center to produce a PtII-CH2R species and a proton.

One possibility is the oxidative addition of a sigma coordinated C-H bond followed by the reductive removal of the proton.

This avoids a problem that plagues many partial oxidation processes, namely, the over-oxidation of substrate to thermodynamic sinks such as H2O and CO2.

It is important that the oxidant preferentially oxidizes the PtII-CH2R species over the initial PtII species since PtIV complexes will not electrophilically activate a C-H bond of the alkane (although PtIV complexes electrophilically substitute hydrogens in aromatics - see refs.

Shilov cycle The overall charge is omitted from the complexes since the exact coordination sphere of the active species is unknown.