om5007177_si_002.cif (12.68 MB)

Nickel(II) Pincer Carbene Complexes: Oxidative Addition of an Aryl C–H Bond to Form a Ni(II) Hydride

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posted on 26.01.2015, 00:00 by Ellen M. Matson, Gabriel Espinosa Martinez, Abdulrahman D. Ibrahim, Bailey J. Jackson, Jeffrey A. Bertke, Alison R. Fout
The synthesis and characterization of a series of nickel­(II) pincer complexes of the meta-phenylene-bridged bis-N-heterocyclic DIPPCCC ligand framework are reported. Characterization of the Ni­(II)Cl complex revealed a square planar species with Cl and the anionic carbon trans to one another. Formation of Ni­(II) alkyl complexes derived from complex 1 was accomplished by addition of LiR [R = CH3 (2); CH2SiMe3 (3)]. Furthermore, we report a synthetic pathway to access the catalytically relevant Ni­(II)H species (DIPPCCC)­NiH (4), by direct oxidative addition of an aryl C–H bond across a Ni(0) center. Complexes 14 have been characterized by 1H and 13C NMR and electronic absorption spectroscopies as well as X-ray crystallography.