The electrostatic nature of bonding in lanthanides provides an opportunity to synthesize complexes of varying coordination number with the same ligand set. The coordination sphere of the early Ln(III) ions (Ln = La - Sm) is especially versatile, exhibiting the ability to form 8-, 9-, and 10-coordinate complexes using the same ligands. Initially, we investigated accessing 8-coordinate Ln(hfac)3(bpy) and 10-coordinate Ln(hfac)3(bpy)2 complexes from Ln(hfac)3(H2O)3 precursors using a mechanochemical approach. These initial studies showed that only the 8-coordinate Sm(hfac)3(bpy) was obtained cleanly. Since this initial study, we have since investigated the effects of ball-milling, the addition of small amounts of solvent and the use of different precursors to increase the efficiency of mechanochemical reactions without requiring further purification. We compare the crude reactions obtained from these syntheses using IR spectroscopy, NMR spectroscopy and melting points using products from conventional solution synthesis as benchmarks.

Investigating mechanochemical approaches for the synthesis of lanthanide complexes

2019 Spring National Meeting

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