The Electronic Properties of Ni(PNN) Pincer Complexes Modulate Activity in Catalytic Hydrodehalogenation Reactions

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Abstract
Three chloronickel(II) complexes of PNN‐ pincer ligands with pyrazolyl and diphenylphosphino donors appended to different arms of diarylamido anchors were prepared and fully characterized. The three derivatives (1‐OMe, 1‐Me, 1‐CF3) differ only by the identity of the para‐aryl substituent on the pyrazolyl arm with 1‐OMe being 310 mV easier to oxidize than 1‐CF3. All three complexes are competent catalysts for hydrodehalogenation reactions of 1‐bromooctane and a variety of aryl halides in dimethylacetamide using NaBH4 as both base and hydride source. Comparative studies using diverse substrates showed that catalytic activity correlates with electron donor properties; 1‐OMe was superior to the other two. Deuterium labeling studies verified NaBD4 as the deuteride source and excluded solvent‐assisted radical pathways.
Funding Information
  • American Chemical Society Petroleum Research Fund (58705‐ND3)

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