Brønsted acid-promoted C–F bond activation in [P, S]-ligated neutral and anionic perfluoronickelacyclopentanes. Issue 45 (24th September 2015)

• Record Type: Journal Article
• Authors: Giffin, Kaitie A.; Korobkov, Ilia; Baker, R. Tom
• Is Part Of: Dalton transactions. Volume 44:Issue 45(2015)
• Page Start: 19587
• Page End: 19596
• Publication Date: 2015-09-24
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt02912k
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Bidentate phosphinothiol ligand induces C–F bond functionalization in perfluoronickelacycles. Abstract : Treatment of L2 Ni(CF2 )4 4a–c (L = PPh3, PPh2 Me, pyridine) with an external Lewis acid (trimethylsilyl triflate) gives new L-functionalized fluoronickelacyclopentanes5a–c . Complexes L2 Ni(CF2 )4 4a, b react with the thiol form of the bidentate ligand 1, 2, 4-(HS)(Ph2 P)Me(C6 H3 )[P, SH] through a unique Brønsted acid-promoted Cα –F bond activation mechanism, affording phosphine-functionalized nickelacycles bearing a phosphinothiolate ligand6a–b . Furthermore, substituting monodentate ligands in L2 Ni(CF2 )4 4a–c with the deprotonated form of the bidentate ligand[P, S − ] leads to the first anionic perfluoronickelacycle7 . The anionic metallacyle reacts with phosphonium salts [PHPh3 ](Br) and [PHPh2 Me](Br) to yield HF and phosphine-functionalized nickelacycles6a, b that still contain the terminal thiolate moiety.