Many chemical and industrial processes utilize precious metal catalysts to facilitate a variety of important reactions and syntheses. Despite their thermodynamic and regioselective benefits, precious metals are relatively scarce, expensive, and toxic to the environment, necessitating research into more sustainable and environmentally viable alternatives. First-row transition metals, albeit presenting their own challenges, provide a suitable alternative due to their abundant, inexpensive nature and relative lack of toxicity. To this end, a mixed donor N2P2 tetradentate ligand composed of two pendant diisopropylphosphines attached to a β-diketiminate backbone via two methoxy-substituted phenyl linkers was synthesized to shuffle electron density onto the metal and increase ligand-metal orbital overlap, stabilizing the metal. Methoxy substituents were utilized to enable exploration of differential steric and inductive electronic effects in comparison with previous methyl and dimethyl versions. Ligands were metallated with iodide salts of Co(II) and Ni(II) and chloride salts of Cu(I). Subsequent characterization of these metal-ligand complexes occurred via NMR spectroscopy, UV-vis spectroscopy, X-ray crystallography, and high-resolution ESI-MS, ultimately elucidating both varied molecular geometry and ligand coordination modes.

Synthesis and characterization of three first-row transition metal complexes supported by a methoxy-substituted N2P2 ligand

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ACS Fall 2022

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