Shilov chemistry alkane reactions

Among catalytic alkane conversions, the most important is the Shilov system and its descendents [108]. Discovered around 1970, these involve Pt(II) salts in aqueous solvents. Initially, the reaction studied was H/D exchange with D2O, where polydeuteration of alkanes was seen. The selectivity for attack at the terminal methyl groups of long chain alkanes made it clear that one was not dealing with classical electrophilic chemistry. The intervention of colloidal Pt was also excluded. 

In the second type of process the metal acts as a carbenoid and inserts into the C—H bond, a process generally termed oxidative addition in organometallic chemistry (equation 1 b). This reaction is believed to go via the same sort of alkane complex as in the Shilov system, but, instead of losing a proton, it goes instead to an alkylmetal hydride. This may be stable, in which case it is observed as the final product, or it may react further. 

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