High‐Valent Oxomanganese Complexes of Relevance in Oxyfunctionalization of Hydrocarbons

Abstract

Abstract Selective activation of inert and ubiquitous CH bonds is one of the most challenging reactions in synthetic organic chemistry. Nature utilizes earth‐abundant paramagnetic metals to bind molecular oxygen and forms reactive high‐valent metal–oxo intermediates, which in turn, cleave strong CH bonds. A large number of biomimetic metal–oxo transients have been successfully synthesized in the last few decades, and many of these have shown promising reactivity toward oxyfunctionalization of hydrocarbons. The field is largely dominated by iron and manganese complexes supported by heme or nonheme ligands. Manganese, albeit of little significance in biological oxidation reactions, can generate high‐valent oxo transients to achieve stoichiometric and catalytic CH and CC activation. Reactivity studies in tandem with spectroscopic and computational analyses have endowed important insights onto the energetics of the oxomanganese transients. Oxidative reactivity of the high‐valent oxomanganese complexes has been shown to be influenced by secondary interactions, redox potentials, and metal–oxo basicity In this article, we highlight notable advances made in the high‐valent oxomanganese chemistry, with special emphasis on their reactivity in oxidation reactions, which include hydroxylation of alkanes and epoxidation of olefins.