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<p>Porous catalysts have garnered substantial interest as potential platforms for
group-transfer catalysis due to the ability to site-isolate catalysts and to non-covalently co-
localize substrates in proximity to reactive intermediates. In contrast to soluble molecular
catalysts, the limited synthetic toolbox available to prepare porous catalysts presents a
formidable challenge to controlling the primary coordination sphere of lattice-confined
catalysts and thus modulating the electronic structures of reactive catalyst intermediates.
Here, we utilize Sonogashira cross-coupling chemistry to prepare a family of porous
metallopolymers, in which the primary coordination sphere of Ru2 sites is systematically
varied. The newly synthesized materials are characterized by IR, elemental analysis, gas
sorption, powder X-ray diffraction, thermogravimetric analysis, X-ray absorption
spectroscopy, and diffuse-reflectance UV-vis-NIR spectroscopy. The resulting porous
materials are catalysts for nitrene-transfer chemistry and the chemoselectivty for allylic
amination of olefin aziridination can be tuned by modulating the primary coordination
sphere of the catalyst sites. The demonstration of metallopolymerization as a rational
synthetic strategy allows to translate ligand-modulated chemoselectivity to porous
catalysts, which represents a new opportunity to tailor the functionality of heterogeneous
analogues of molecular complexes.
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Metallopolymerization as a Strategy to Translate Ligand-Modulated Chemoselectivity to Porous Catalysts