A Ru–porphyrin metal–organic framework with Mn2+ paddlewheel nodes for the selective oxidation of C(sp3)–H bonds

Abstract

The activation and selective functionalization of inert C(sp³)–H bonds is fundamental for industrial applications and occupies a very important place in industry, but it remains a great challenge in current synthetic chemistry. In this paper, we report an approach for activating reactive tert-butyl peroxyl radicals by modifying Ru–porphyrin into metal–organic frameworks (MOFs) for the activation of inert C(sp³)–H bonds. Under mild conditions, the Ru–porphyrinyl MOF can activate the peroxyl radical, extracting a hydrogen atom from the inert C(sp³)–H bond. Mn²⁺ paddlewheels with unsaturated coordination sites were introduced into the MOF, and direct oxidative conversion using environmentally friendly oxygen provides a new pathway to activate the inert C(sp³)–H bond.