Vanadium(V IV )-Porphyrin-Based Metal-Organic Frameworks for Synergistic Bimetallic Activation of Inert C(sp 3 )-H Bonds.

Activation and selective functionalization of inert C(sp 3 )-H bonds remain one of the most challenging tasks in current synthetic chemistry. Herein, by decorating vanadium(V IV )-porphyrin into metal-organic frameworks (MOFs) to stabilize the active tertbutyl peroxide radical, we reported a new approach to accomplish inert C(sp 3 )-H bond activation by a synergistic bimetallic strategy via a hydrogen atom transfer process under mild conditions. The stabilized peroxide radical by V IV -porphyrin-based MOFs abstracted a hydrogen atom from the inert C(sp 3 )-H bonds for direct oxidization transformation utilizing environmentally friendly oxygen. Taking advantage of the high stability of Zr 6 clusters, the new Zr-MOF was recyclable six times without a conversion efficiency decrease. From this foundation, {Mn 3 (μ 3 -O)} cluster nodes with potential unsaturated coordinated sites were introduced into MOFs to replace Zr 6 clusters, realizing the pre-activation of substrates through the interaction between Mn nodes and substrates. The synergistic bimetallic activation effect of V IV -porphyrin and Mn nodes dramatically promoted the conversion efficiency and product selectivity for inert C(sp 3 )-H bond functionalization.