Nonheme mono- and dinuclear iron complexes in bio-inspired C-H and C--C bond hydroxylation reactions: Mechanistic insight

The selective catalytic functionalization of hydrocarbons under mild conditions is a subject of considerable current interest. While selective oxidations of C-H bonds remain a challenging task to the synthetic chemists, Nature provides several successful solutions to this by utilizing remarkably efficient biocatalysts, namely the oxygenases. Iron-containing oxygenases with heme or nonheme active sites participate in biologically important oxidative transformation reactions by dioxygen activation. The transient high-valent iron-oxo species thus generated are proposed to be the key reactive intermediates in the oxidation reactions and have been detected in several occasions. Inspired by the Nature, rational design of synthetic analogues of iron oxygenases paves the way for the development of efficient catalysts for selective C-H bond oxidation. This review focuses on the significant advances made in the catalytic oxidations of hydrocarbons by different nonheme mono- and dinuclear iron complexes over past three decades with a highlight on the mechanistic aspects and addresses the forthcoming challenges in this field.

Automated summary

Iron-oxo species are proposed to be the key reactive intermediates in the selective oxidation of C-H bonds. The rational design of synthetic analogues of iron oxygenases opens up possibilities for the development of efficient catalysts for selective C-H bond oxidation.