Brønsted acid-promoted C-F bond activation in [P,S]-ligated neutral and anionic perfluoronickelacyclopentanes
Kaitie A Giffin1, Ilia Korobkov, R Tom Baker
1Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa, 30 Marie Curie, Ottawa, ON K1N 6N5, Canada. rbaker@uottawa.ca.
Abstract:
Treatment of L2Ni(CF2)44a-c (L = PPh3, PPh2Me, pyridine) with an external Lewis acid (trimethylsilyl triflate) gives new L-functionalized fluoronickelacyclopentanes 5a-c. Complexes L2Ni(CF2)44a,b react with the thiol form of the bidentate ligand 1,2,4-(HS)(Ph2P)Me(C6H3) [P,SH] through a unique Brønsted acid-promoted Cα-F bond activation mechanism, affording phosphine-functionalized nickelacycles bearing a phosphinothiolate ligand 6a-b. Furthermore, substituting monodentate ligands in L2Ni(CF2)44a-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.
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