Coordination and oxidative addition of octafluoronaphthalene at a nickel centre: isolation of an intermediate in C–F bond activation

Selective CF Bond Activation of Tetrafluorobenzenes by Nickel(0) with a Nitrogen Donor Analogous to N‐Heterocyclic Carbenes

“…To test the ability of these ligands to aid in the oxidative addition of challenging substrates, we investigated the activation of the strong and relatively inert CÀF bonds [18][19][20][21] in fluorinated aromatics by nickel(0). [22][23][24][25][26][27][28][29][30] It is known that sources of the {(PEt 3 ) 2 Ni} moiety react with the tetrafluorobenzenes, but the reaction takes weeks at room temperature and can provide unwanted byproducts by rapid and reversible CÀH bond activation. [31] Very recently it has been shown that the use of N-heterocyclic carbenes rather than phosphines as the ancillary ligand in these reactions allows for more rapid selective activation of C À F bonds in a variety of polyfluorobenzene species; however, to date no nickel complex capable of the selective activation of the tetrafluorobenzenes has been reported.…”

Conversion of Carbon–Fluorine Bonds α to Transition Metal Centers to Carbon–Hydrogen, Carbon–Carbon, and Carbon–Heteroatom Bonds

“…B-F, Si-F, or H-F bonds, [21,93] bonds between early transition metals or actinides and fluorine, [94] or ionic metal fluorides. [8,[95][96] Aromatics can be readily activated by oxidative addition of the C-F bond via an η 2 -arene intermediate [8,47,[49][50][51][52][97][98][99][100][101][102][103][104][105][106][107][108][109][110][111] or by addition/elimination using metal nucleophiles. [8,51,[112][113] Likewise, some fluorinated alkenes have yielded to C-F bond activation.…”

Organometallic chemistry using partially fluorinated benzenes

“…While the reaction of FB with {NiL 2 } has yet to be observed, not only does 1fluoronaphthalene react with [Ni(PCy 3 ) 2 ] to form the corresponding oxidative addition product, 115 detailed studies on the addition of perfluoronaphthalene to [Ni(PEt 3 ) 2 ] have allowed the identification of the η 2 -complex as a reaction intermediate in the oxidative addition pathway (Scheme 10). 116 The focus on 1 st row d 10 complexes undoubtedly stems from the increased dπ-2pπ repulsion, and associated decrease in metal-fluorine bond strengths, as the triad is descended and the d-orbitals gain radial extension. 5 Pd-and Pt-complexes, while known for C-F bond activation, are less widely employed than those of Ni.…”