A Ru-porphyrin metal-organic framework with Mn 2+ paddlewheel nodes for the selective oxidation of C(sp 3 )-H bonds.

The activation and selective functionalization of inert C(sp 3 )-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(sp 3 )-H bonds. Under mild conditions, the Ru-porphyrinyl MOF can activate the peroxyl radical, extracting a hydrogen atom from the inert C(sp 3 )-H bond. Mn 2+ 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(sp 3 )-H bond.