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Actinide–Oxygen Multiple Bonds from Air: Synthesis and Characterization of a Thorium Oxo Supported by Redox-Active Ligands
23
Citations
44
References
2022
Year
The first non-uranyl, f-element oxo complex synthesized from dioxygen in dry air is presented in this work. The synthesis was accomplished by treating the redox-active thorium amidophenolate complex, [Th(<sup>dipp</sup>ap)<sub>3</sub>][K(15-<i>c</i>-5)<sub>2</sub>]<sub>2</sub> (<b>1-ap crown</b>), with dioxygen in dry air, forming a rare terminal thorium oxo, [O═Th(<sup>dipp</sup>isq)<sub>2</sub>(<sup>dipp</sup>ap)][K(15-<i>c</i>-5)<sub>2</sub>]<sub>2</sub> (<b>2-oxo</b>). Compound <b>1-ap crown</b> was regenerated by treating <b>2-oxo</b> with potassium graphite. X-ray crystallography of <b>2-oxo</b> revealed a comparatively longer bond length for the thorium-oxygen double bond when compared to other thorium oxos. As such, several thorium-oxygen single bonds were synthesized for comparison, including Th(<sup>dipp</sup>isq)<sub>2</sub>(OSiMe<sub>3</sub>)<sub>2</sub>(THF) (<b>4-OSiMe</b><sub><b>3</b></sub>), Th(OSiMe<sub>3</sub>)<sub>4</sub>(bipy)<sub>2</sub> (<b>5-OSiMe</b><sub><b>3</b></sub>), and [Th(OH)<sub>2</sub> (<sup>dipp</sup>Hap)<sub>4</sub>][K(15-<i>c</i>-5)<sub>2</sub>]<sub>2</sub> (<b>6-OH</b>). Full spectroscopic and structural characterization of the complexes was performed via <sup>1</sup>H NMR spectroscopy, X-ray crystallography, EPR spectroscopy, and electronic absorption spectroscopy as well as SQUID magnetometry, which all confirmed the electronic structure of these complexes.
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