Abstract
Treatment of L2Ni(CF2)(4) 4a-c (L = PPh3, PPh2Me, pyridine) with an external Lewis acid (trimethylsilyl triflate) gives new L-functionalized fluoronickelacyclopentanes 5a-c. Complexes L2Ni(CF2)(4) 4a, b react with the thiol form of the bidentate ligand 1,2,4-(HS)(Ph2P) Me(C6H3) [P,SH] through a unique Bronsted acid-promoted Ca-F bond activation mechanism, affording phosphine-functionalized nickelacycles bearing a phosphinothiolate ligand 6a-b. Furthermore, substituting monodentate ligands in L2Ni(CF2)(4) 4a-c with the deprotonated form of the bidentate ligand [P, S-] leads to the first anionic perfluoronickelacycle 7. The anionic metallacyle reacts with phosphonium salts [PHPh3](Br) and [PHPh2Me](Br) to yield HF and phosphine-functionalized nickelacycles 6a, b that still contain the terminal thiolate moiety.