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Synthesis

Convenient Access To Thorium Chemistry

A trio of new anhydrous complexes boosts thorium’s prospects in catalysis, materials science, and as a nuclear fuel

by Stephen K. Ritter
February 1, 2010 | A version of this story appeared in Volume 88, Issue 5

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Credit: Chem. Commun.
Credit: Chem. Commun.

The burgeoning use of nonaqueous thorium chemistry in catalysis and materials science could benefit from a trio of anhydrous thorium complexes created by a team of Los Alamos National Laboratory chemists (Chem. Commun., DOI: 10.1039/b923558b). The complexes also could improve the prospects for developing thorium-based nuclear-power reactors (C&EN, Nov. 16, 2009, page 44). Anhydrous halide complexes are key starting points for synthesizing transition-metal, lanthanide, and actinide compounds. However, preparing thorium halides is hampered by tricky reactions that require harsh conditions and scarce thorium metal. Seeking a better approach, Thibault Cantat, Brian L. Scott, and Jaqueline L. Kiplinger refluxed commercially available thorium nitrate, Th(NO3)4(H2O)5, with 12 M 
HCl to produce ThCl4(H2O)4 in quantitative yield under mild conditions. The team then used a novel combination of anhydrous HCl and (CH3)3SiCl to remove the coordinated water molecules and replace them with dimethoxyethane (DME), 1,4-dioxane, or tetrahydrofuran solvent molecules to make the three new reagents. Kiplinger and coworkers demonstrated the versatility of ThCl4(DME)2 by using it to prepare thorium alkoxide, amide, metallocene, and other compounds on multigram scales.

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