Peroxo-Thorium(IV)-Containing Heteropolytungstates and Their Oxo-Analogues: Synthesis, Structure and Solution Studies
We report the synthesis of peroxo-thorium(IV)-containing silico- and germanotungstates, [Th<sub>3</sub>(μ<sub>3</sub>-O<sub>2</sub>)(OH)<sub>2</sub>(H<sub>2</sub>O)<sub>3</sub>(<i>A-</i>α-XW<sub>9</sub>O<sub>34</sub>)<sub>2</sub>]<sup>12-</sup> (X = Si, <b>Th</b><sub><b>3</b></sub><b>O</b><sub><b>2</b></sub><b>Si</b>; Ge, <b>Th</b><sub><b>3</b></sub><b>O</b><sub><b>2</b></sub><b>Ge</b>), prepared in aqueous solution via a straightforward two-step procedure: (1) reaction of thorium(IV) cations with trilacunary polytungstate precursors, followed by (2) the addition of hydrogen peroxide. In the absence of hydrogen peroxide, we were able to obtain the oxo-analogues, [Th<sub>3</sub>(μ<sub>3</sub>-O)(OH)<sub>3</sub>(H<sub>2</sub>O)(<i>A-</i>α-SiW<sub>9</sub>O<sub>34</sub>)<sub>2</sub>]<sup>13-</sup> (<b>Th</b><sub><b>3</b></sub><b>Si</b>) and [Th<sub>3</sub>(μ<sub>3</sub>-O)(OH)<sub>3</sub>(<i>A-</i>α-GeW<sub>9</sub>O<sub>34</sub>)<sub>2</sub>]<sup>13-</sup> (<b>Th</b><sub><b>3</b></sub><b>Ge</b>), respectively. All four polyanions crystallized as hydrated mixed rubidium-sodium salts. Single-crystal X-ray diffraction revealed that the four polyanions <b>Th</b><sub><b>3</b></sub><b>O</b><sub><b>2</b></sub><b>Si</b>, <b>Th</b><sub><b>3</b></sub><b>O</b><sub><b>2</b></sub><b>Ge</b>, <b>Th</b><sub><b>3</b></sub><b>Si</b>, and <b>Th</b><sub><b>3</b></sub><b>Ge</b> consist of two {<i>A-</i>α-XW<sub>9</sub>O<sub>34</sub>} fragments sandwiching a central, triangular thorium core. The structures of <b>Th</b><sub><b>3</b></sub><b>O</b><sub><b>2</b></sub><b>X</b> (X = Si, Ge) comprise a central peroxo-group with a rare side-on μ<sub>3</sub>-coordination mode between the three thorium centers, representing the first example of peroxo-thorium(IV)-containing polyoxotungstates. Furthermore, <sup>183</sup>W NMR and electrochemical studies in solution were performed.
Authors
- Bassem S. Bassil (ORCID: https://orcid.org/0000-0002-4978-1245)
- L RUHLMANN
- Sahar Khandan
- Arnulf Materny (ORCID: https://orcid.org/0000-0003-4707-195X)
- Anupam Sarkar
- Ayush K. Ranga
- Samer Dawoud
- Ulrich Kortz
Institutions
- Constructor University (DE)
- Institut de Chimie de Strasbourg (FR)
- Laboratoire de Chimie Physique (FR)
- Institut de Chimie (FR)
- Université de Strasbourg (FR)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2026-01-08
- DOI
- https://doi.org/10.1021/acs.inorgchem.5c04382
- Primary Topic
- Silicone and Siloxane Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.00