Square-planar (Pentafluorophenyl)nickel(II) complexes by derivatization of a C-F activation product

The NHC-stabilized C-F activation product [Ni(iPr(2)Im)(2)(F)-(C6F5)] (1) was isolated from the reaction of [Ni(cod)(2)] with 1,3-diisopropylimidazol-2-ylidene (iPr(2)Im) and hexafluorobenzene. Square-planar (pentafluorophenyl)nickel complexes of the type [Ni(iPr(2)Im)(2)(X)(C6F5)] were obtained by a systematic derivatization of 1. The reaction of 1 with silylated compounds and organyllithium compounds led smoothly to replacement of the fluorido ligand in 1 by halogenido, trifluoromethanesulfonato, cyanido, organyl, selenolato, thiolato, and hydrido ligands. According to these procedures, the NHC-stabilized (pentafluorophenylmickel complexes [Ni(iPr(2)Im)(2)(X)(C6F5)] (X = Cl2, I3, CF3SO3 4, CN 5), (Ni(iPr(2)Im)(2)-(R)(C6F5)] (R = Me 6, Ph 7, C2Ph 8, eta(1)-Cp 9), [Ni(iPr(2)Im)(2)(SR)(C6F5)] (R = Ph 10, nPr 11), [Ni(iPr(2)Im)(2)(SeR)(C6F5)] (R = Ph 12, iPr 13), and [Ni(iPr(2)Im)(2)(H)(C6F5)] (14) were prepared. The complexes 4, 6. 9, 11, 13 and 14 were structurally characterized. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008.