Coinage Metal (Bisfluorosulfonyl)imide Complexes: Preparation, Characterization, and Catalytic Applications

Triflate ( – OTf) and triflimide ( – NTf 2 ) represent two most widely used weakly coordinating counteranions in transition metal catalysis, yet their high price hinders large‐scale application. Herein, we report the preparation, characterization, and catalytic applications of silver(I), gold(I), and copper(II) (bisfluorosulfonyl)imide ( – FSI) complexes, showing – FSI as a low cost alternative of – OTf and – NTf 2 . These complexes, including AgFSI · 2MeCN ( 1 ), AgFSI · MeCN ( 2 ), AgFSI · H 2 O ( 3 ), (AgFSI) 6 · (H 2 O) 4 ( 4 ), AgFSI ( 5 ), LAuFSI ( 6a – 6e ), and CuFSI 2 · 4H 2 O ( 7 ), are prepared conveniently starting from KFSI, an inexpensive chemical, and shown interesting structural features and some unprecedented coordination modes. In comparison with the corresponding coinage metal triflimides, the FSI complexes have exhibited comparable or better catalytic performance in a series of the model chemical transformations.