Shilov alkane platinum chemistry: 45 years

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

“…So-called Shilov chemistry [1,[286][287][288][289][290][291] m-Chloroperbenzoic acid in the presence of certain metal compounds efficiently oxidizes alkanes at low temperature with a very high degree of stereoselectivity (trans/cis << 1) [160,227,284,285]. Apparently, radicals are not produced intermediately in the course of such oxidation, which occurs via a "concerted" mechanism.…”

“…So-called Shilov chemistry [1,[286][287][288][289][290][291] includes two reactions (discovered in 1969 and 1972 [1]). It was demonstrated that Pt II Cl4 2− ion catalyzes H/D exchange in methane in a D2O/CD3COOD solution and, if Pt IV Cl6 2− is added, the latter oxidizes methane to methanol.…”

Regioselective C–H hydroxylation of n-alkanes using Shilov-type Pt catalysis in perfluorinated micro-emulsions

“…Notably, by combining a homogeneous Pt II catalyst with H 2 PtCl 6 as a stoichiometric oxidant, Shilov and co-workers succeeded in conducting the hydroxylation of aliphatic compounds (Scheme 1). [17][18][19] More importantly, the electrophilic nature of this Pt II catalyst allows one to discriminate between non-equivalent C-H bonds in a very different manner than radicals do. Selectivity patterns in Ptmediated Shilov-type reactions therefore show an enhanced reactivity of the remote C-H bonds, together with a reduced degree of overoxidation.…”

“…Selectivity patterns in Ptmediated Shilov-type reactions therefore show an enhanced reactivity of the remote C-H bonds, together with a reduced degree of overoxidation. 19,20 Nevertheless, such Pt chemistry is almost exclusively performed in acidic aqueous solutions, thereby restricting the substrate scope to water-soluble substrates, e.g. alkyl ammonium salts, as well as lower carboxylic, sulfonic and phosphonic acids.…”

Methylpalladium complexes with pyrimidine-functionalized N-heterocyclic carbene ligands

“…Early work by Bergman [ 8 – 9 ] and Graham [ 10 – 11 ] showed that the activation of methane is possible, but their systems provided only stoichiometric reactions. The Shilov system [ 12 – 17 ], had the disadvantage of using stoichiometric amounts of platinum for the reoxidation of the active catalyst and the platinum bispyrimidine system [ 18 – 20 ] was not successful because of the large amounts of diluted sulfuric acids as the byproduct of the methanol synthesis. Sen reported the activity of palladium(II) catalysts for the oxidation of methane [ 21 ] and several groups contributed to the progress in the field which is summarized in recent reviews [ 22 – 23 ].…”