Synthetic methodologies to generate bifunctional, stable ligands on uranium were explored. An end-product with an oxygen-coordinating chelate bound to uranium with a pendant phosphine was envisioned. In order to achieve this goal, a little used reaction that accomplishes a 1,2-addition of a (trimethylsilyl)phosphine across an aldehyde carbonyl bond was pursued. This reaction produces a C-P bond with concomitant O-TMS bond formation. Several dialdehyde starting materials were probed as the scaffolds for this reactivity, and with the use of UCl4 as the actinide starting material. Over the course of these reactions, generation of TMS-Cl was observed, with simultaneous generation of the U-O bond. Color changes indicate stepwise reactivity, with the solution changing colors following the first U-O bond generation, with a second color change to indicate the second TMS-Cl loss and U-O bond formation. The resultant (O-P)UCl3 and (O-O)UCl2 complexes were characterized, and the chelating ligands were crystallized to unambiguously assign the complexes. The peripheral phosphines of the chelate were then used to coordinate transition metals to generate the desired heterobimetallic complexes bearing f- and d-block metals. This represents an alternative methodology to begin looking at metal-containing architectures that span from the molecular to the macromolecular.

Generating ligand scaffolds for mixed f- and d-block heterobimetallic architectures

ACS Spring Meeting 2021

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