Activation of C–F and Ni–C Bonds of [P,S]-Ligated Nickel Perfluorometallacycles

Abstract

The first example of a [P,S]-ligated metal perfluorocyclopentane is reported. The new metallacycle undergoes Cα–F activation in the presence of a Lewis acid, followed by chemoselective ligand migration, affording a fused metallabicyclic product. Reactivity of this product includes an unprecedented nucleophile-induced ring-opening reaction, involving loss of a β-fluoride. Additionally, hydrolysis of the metallabicyclic product affords a single isomer of hexafluoro-1-butene.

A T-shaped Ni[κ2-(CF2)4–] NHC complex: unusual Csp3–F and M–CFbond functionalization reactions

“…Starting from bis(phosphite) PNCPs 10 ( 1a and b ) we were able to cleanly synthesize coordinatively-saturated or -unsaturated nickel perfluorometallacycles. Thus, 1a reacts smoothly with 1 equiv.…”

“… 9 Extending this reaction to the unsymmetrical P^S chelate, we showed that treatment with excess isonitrile effected cleavage of the Ni–C F bond ( Scheme 2b ). 10 With phosphite co-ligands, a remarkable hydrogenolysis reaction enables the selective catalytic hydrodimerization of TFE ( Scheme 2c ). 11 As far as we know, this reaction is the only example of a perfluoro-metallacyclopentane participating in a catalytic cycle.…”

Gold Complexes with Difunctional Perfluoroalkyl Chains: Quantifying the Energy of Aurophilic Interactions in Flexible Open‐Chain Complexes

“…[31] Fluorinated metallacyclopentanes have been obtained by cyclodimerization of fluorinated ethenes (F), [22,[32][33][34][35][36][37][38] or cocyclodimerization of C 2 F 4 and C 2 H 4 (G), [39,40] on electron-rich metal centres. Their unusual reactivity [41][42][43][44] illustrates the potential of C 2 F 4 in the synthesis of valuable fluoroorganic compounds. [37,39,40] Only a few perfluorometallacycles with n ¼ 6 4 have been reported.…”

Nickel(0)‐Mediated Transformation of Tetrafluoroethylene and Vinylarenes into Fluorinated Cyclobutyl Compounds

“…Burch and co‐workers reported pioneering work wherein α‐fluorine elimination in [(PEt 3 ) 2 Ni(CF 2 ) 4 ] was promoted by the addition of BF 3 ⋅Et 2 O to give (PEt 3 )(BF 4 )Ni[CF(PEt 3 )(CF 2 ) 3 ] as a result of the migration of one of the PEt 3 ligands to the transient fluorocarbene intermediate . Baker further demonstrated the transformation of [(SIPr)Ni(CF 2 ) 4 ] into perfluorocyclobutene and isolated its reaction intermediate (Scheme a) ,…”