| Summary: | Separate reactions of [Th{N(CH<sub>2</sub>CH<sub>2</sub>NSiMe<sub>2</sub>Bu<sup>t</sup>)<sub>2</sub>(CH<sub>2</sub>CH<sub>2</sub>NSi(Me)(Bu<sup>t</sup>)(μ-CH<sub>2</sub>)]<sub>2</sub> (<b>1</b>) with [Re(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>(H)] (<b>2</b>) or [Ru(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(H)(CO)<sub>2</sub>] (<b>3</b>) produced, by alkane elimination, [Th(Tren<sup>DMBS</sup>)Re(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>] (<b>ThRe</b>, Tren<sup>DMBS</sup> = {N(CH<sub>2</sub>CH<sub>2</sub>NSiMe<sub>2</sub>Bu<sup>t</sup>)<sub>3</sub>}<sup>3-</sup>), and [Th(Tren<sup>DMBS</sup>)Ru(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(CO)<sub>2</sub>] (<b>ThRu</b>), which were isolated in crystalline yields of 71% and 62%, respectively. Complex <b>ThRe</b> is the first example of a molecular Th-Re bond to be structurally characterised, and <b>ThRu</b> is only the second example of a structurally authenticated Th-Ru bond. By comparison to isostructural U-analogues, quantum chemical calculations, which are validated by IR and Raman spectroscopic data, suggest that the Th-Re and Th-Ru bonds reported here are more ionic than the corresponding U-Re and U-Ru bonds.
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