Direct base-assisted C‒H cyclonickelation of 6-phenyl-2,2'-bipyridine

Nicolas Vogt, Vasily Sivchik, Aaron Sandleben, Gerald Hörner, Axel Klein

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6 Citations (Scopus)
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Abstract

The organonickel complexes [Ni(Phbpy)X] (X = Br, OAc, CN) were obtained for the first time in a direct base-assisted arene C(sp2)-H cyclometalation reaction from the rather unreactive precursor materials NiX2 and HPhbpy (6-phenyl-2,2'-bipyridine) or from the versatile precursor [Ni(HPhbpy)Br2]2. Different from previously necessary C‒Br oxidative addition at Ni(0), an extended scan of reaction conditions allowed quantitative access to the title compound from Ni(II) on synthetically useful timescales through base-assisted C‒H activation in nonpolar media at elevated temperature. Optimisation of the reaction conditions (various bases, solvents, methods) identified 1:2 mixtures of acetate and carbonate as unrivalled synergetic base pairs in the optimum protocol that holds promise as a readily usable and easily tuneable access to a wide range of direct nickelation products. While for the base-assisted C‒H metalation of the noble metals Ru, Ir, Rh, or Pd, this acetate/carbonate method has been established for a few years, our study represents the leap into the world of the base metals of the 3d series.

Original languageEnglish
Article number997
Number of pages13
JournalMolecules
Volume25
Issue number4
DOIs
Publication statusPublished - 24 Feb 2020

Keywords

  • 6-PHENYL-2,2-BIPYRIDINE
  • ACTIVATION
  • BONDS
  • C-H activation
  • CRYSTAL-STRUCTURE
  • FUNCTIONALIZATION
  • LIGAND
  • NICKEL(II) COMPLEXES
  • PALLADIUM(II)
  • PLATINUM
  • PT-II
  • base-assisted
  • cyclometalation
  • cyclonickelation
  • organonickel

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