Traditional oxidizing agents (e.g. hexavalent chromium) are costly, carcinogenic, and pose significant environmental hazards.  Therefore, it is desirable to use molecular oxygen as an alternative oxidizing agent, but the challenge is to develop catalysts which can activate molecular oxygen.  Ni(II) complexes are unlikely candidates, due to the inaccessibility of higher oxidation states for nickel, but ligands with oxime functional groups can lower the oxidation potential.  Baldwin and coworkers have synthesized nickel(II) complexes with ligands containing three oxime functional groups, specifically tris(1-propan-2-onyl oxime)amine (H3TRISOX).This study has examined the effects of modifying the polyoximate ligand to form a more sterically shielded complex.   Our TRIPHOX ligand substitutes the three methyl groups on TRISOX with phenyl groups, while our TRITOX ligand has tert-butyl groups. Oxidations using the complex Ni(H3TRIPHOX)Cl2 have been carried out with a variety of alcohols in several solvents.  The oxidation products were characterized by FT-IR and 1H-NMR.

Synthesis of nickel(II) complexes with tri-oxime ligands to be oxygen-activating catalysts

243rd National Meeting (2012)

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