The incorporation of bifunctional ligands onto a 3d transition metal center has shown to be a promising route to produce complexes with catalytic performances comparable to the their 4d and 5d metal counterparts. However, there are very few reports regarding systematic studies of the structure-property relationships for 3d metal complexes in the literature, likely restricting their application. A possible explanation may be the limited synthetic routes available to attain multiple systematically varied ligand analogs necessary for this type of study. We report a modular synthesis to generate a library of bidentate aminophosphine-pyridine ligands prepared from commercially available precursors. The ligand library is structured to study the effect metallacycle size and phosphorus substituents (electronic and steric properties) have on the hemilability and acidic/basic/hydrogen-bonding nature of the aminophosphine with multiple 3d metals. The metals’ hard-soft properties are being explored through the ambidentate nature of the aminophosphine moiety. Currently, the ligand synthesis and coordination to M(II) species are being optimized, but initial studies have shown NiCl<sub>2</sub> to preferentially coordinate to the pyridine and phosphorus atom of the aminophosphine, adopting a high spin, tetrahedral geometry. In some cases, the aminophosphine terminus was observed to be hemilabile, allowing bifunctional activation of protic acids: the aminophosphine accepting a proton and decoordinating, allowing the counterion to bind to the metal center.

Modular, single-step synthesis of systematically varied monoprotic aminophosphine ligands: Studying fundamental concepts in 3D transition metal chemistry

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.