Many industrial processes use precious metals as catalysts due to their selectivity and stability. Recent research has explored the possibility of using first-row transition metals as sustainable, affordable, and abundant alternatives to current precious metals. As a result, a family of tetradentate mixed-donor ligands has been synthesized and metalated with first-row transition metals. The N2P2 tetradentate ligand contains two pendant phosphine atoms on phenyl linker groups and a β-diketiminate backbone. Methyl, methoxy, and dimethyl groups were substituted on the phenyl linkers to explore different steric and electronic effects. Initial metalation studies with zinc iodide showed two different binding modes. In the case of methyl and methoxy substituted ligands, the zinc metal was bound in a κ4 fashion to the ligand. In the dimethyl substituted ligand, however, a κ3 binding mode was observed. Most recently, the metalation scope has been expanded to halide salts of Co(II), Ni(II), and Cu(I). The binding modes, along with the synthesis and characterization methods of these new complexes, will be discussed.

Synthesis of first-row transition metal complexes using a family of N2P2 ligands

ACS Spring 2022

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