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.