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

Zhenzhong LiHuating JiangJinxiu LiuTiantian NingNam Thanh Son PhanFang Zhang
Published in: ACS applied materials & interfaces (2022)
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 (Rh 2 -ZIF-8). The active sites in Rh 2 -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 Rh 2 (esp) 2 (2-MeIm) 1 configuration was able to exhibit obviously enhanced selectivity compared to homogeneous catalyst Rh 2 (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.
Keyphrases
  • metal organic framework
  • oxide nanoparticles
  • crystal structure
  • wastewater treatment
  • molecular dynamics simulations
  • molecular dynamics
  • gold nanoparticles
  • ionic liquid
  • structural basis