Metal-organic layers as reusable solid fluorination reagents and heterogeneous catalysts for aromati

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Reusable solid fluorination reagents and heterogeneous catalysts are ideally suited for late-stage fluorination with fast and clean conversion and simplified work-up.Here we report Pd-functionalized two-dimensional metal-organic layers (MOLs) as solid reagents and heterogeneous catalysts to efficiently fluorinate a broad scope of aromatic compounds.Site isolation in the MOLs provides a unique opportunity to stabilize highly active F-containing species for the chemical conversion.A terpyridine (TPY)-based ligand on the MOL,together with a 2-chloro-1,10-phenanthroline (phenCl) as a co-ligand,chelates PdⅡ to form a reactive center.After treatment with Selectfluor/H2O,an (N-fluoroxy)-(2-chloro)-phenanthrolinium[N-(FO)-phenCl+]moiety is produced from the co-ligand on the Pd center.This active species serves as a stochiometric solid fluorination reagent,which shows different regioselectivities and reactivities as compared to homogeneous catalysts that involves PdⅢ/Ⅳ-F intermediates in catalytic cycles.The MOLs can also be used as heterogeneous catalysts for fluorination using Selsctfluor.This work highlights opportunities in using MOLs to stabilize unique active sites for late-stage fluorination.
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