Shilov alkane platinum chemistry: 45 years

• Alex Shilov, one of the pioneers of homogeneous metal complex alkane activation, was a wise teacher and great friend of the author.
• The beginning was hard and exciting and the author remembers it as the best years of his life.
• The discovery of homogeneous alkane activation at 1960s was a starting point of new field of metal complex catalysis.
• The activation of alkanes in solutions of transition metal complexes is a chemical model of anaerobic methane oxidation in nature.
• The mechanism of enzymatic anaerobic methane oxidation is unknown until now.

In this essay the author shares his recollections and thoughts about the early stages of development of the alkane platinum chemistry known today under the name “Shilov chemistry”.

Shilov reaction involves several stages: (A) the alkane molecule enters the metal coordination sphere to form the σ-complex M…RH, (B) a cleavage of the C–H bond forms methylhydride intermediate which in the next stage (C) spontaneously releases H+, and the PtII-activated alkane transforms into functional derivatives with the use of different terminal oxidants, for example, [PtCl6]2− (D-E).Figure optionsDownload as PowerPoint slide