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Nano Research

Article Title

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

Authors

Wenjie Shi, State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Production of Alcohols, Ethers and Esters, Department of Chemistry, College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005, China;Department of Chemistry, University of Chicago, Chicago, IL 60637, USA
Lingzhen Zeng, State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Production of Alcohols, Ethers and Esters, Department of Chemistry, College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005, China
Lingyun Cao, State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Production of Alcohols, Ethers and Esters, Department of Chemistry, College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005, China
Ying Huang, State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Production of Alcohols, Ethers and Esters, Department of Chemistry, College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005, China
Cheng Wang, State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Production of Alcohols, Ethers and Esters, Department of Chemistry, College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005, China
Wenbin Lin, Department of Chemistry, University of Chicago, Chicago, IL 60637, USA

Keywords

metal-organic layers, solid reagent, heterogeneous catalyst, fluorination

Abstract

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 Selectfluor. This work highlights opportunities in using MOLs to stabilize unique active sites for late-stage fluorination.

Publisher

Tsinghua University Press

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