Self-Adaptive Dirhodium Complexes in a Metal–Organic Framework for Synthesis of N–H Aziridines

Conformational dynamics of active sites in enzymes enable great control over the catalytic process. Herein, we constructed a metal–organic framework with conformationally dynamic active sites (Rh2-ZIF-8). The active sites in Rh2-ZIF-8 were composed of the imidazolate-bridged bimetallic center with a catalytic dirhodium moiety and structural zinc site. Even though the coordination sphere of the dirhodium species was saturated with two circularly arranged esp groups and two axial 2-MeIm ligands, it could still effectively catalyze the direct synthesis of N–H aziridines from olefins with high activity. We found that such a self-adaptive catalytic process was based on the dynamic breakage and reformation of the rhodium–zinc imidazolate bridges. Interestingly, the in situ generated dirhodium site with a unique Rh2(esp)2(2-MeIm)1 configuration was able to exhibit obviously enhanced selectivity compared to homogeneous catalyst Rh2(esp)2. Furthermore, the surrounding zinc imidazolate groups could effectively protect the dirhodium moieties from harsh environments, and this ultimately endowed it with high stability.