The Role of Higher Oxidation State Species in Platinum-Mediated C-H Bond Activation and Functionalization

The Shilov system, a mixture of di- and tetravalent chloroplatinate salts in aqueous solution, provided the first indication of the potential of organotransition metal complexes for activating and functionalizing alkanes under mild conditions; the participation of higher-valent species plays a crucial role. In this chapter, we discuss the experimental and computational studies that have led to detailed mechanistic understanding of C-H activation and functionalization by both the original Shilov system and the many subsequent modifications that have been developed, and assess the prospects for practical, selective catalytic oxidation of alkanes using this chemistry.