Accessing Pincer Bis(carbene) Ni(IV) Complexes from Ni(II) via Halogen and Halogen Surrogates

This communication describes the two-electron oxidation of ((DIPP)CCC)NiX ((DIPP)CCC = bis(diisopropylphenyl-benzimidazol-2-ylidene)phenyl); X = Cl or Br) with halogen and halogen surrogates to form ((DIPP)CCC)NiX3. These complexes represent a rare oxidation state of nickel, as well as an unprecedented reaction pathway to access these species through Br2 and halogen surrogate (benzyltrimethylammonium tribromide). The Ni(IV) complexes have been characterized by a suite of spectroscopic techniques and can readily reduce to the Ni(II) counterpart, allowing for cycling between the Ni(II)/Ni(IV) oxidation states.