Tetrazenyl-, Imido-, and Azidoaluminate Derivatives of a Sterically Demanding Bis-Silazide Ligand
The potassium alumanyl [{SiN<sup>Dipp</sup>}AlK]<sub>2</sub> (SiN<sup>Dipp</sup> = {CH<sub>2</sub>SiMe<sub>2</sub>NDipp}<sub>2</sub>; Dipp = 2,6-<i>i</i>-Pr<sub>2</sub>C<sub>6</sub>H<sub>...
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| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-01-01
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| Series: | Inorganics |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2304-6740/13/1/25 |
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| Summary: | The potassium alumanyl [{SiN<sup>Dipp</sup>}AlK]<sub>2</sub> (SiN<sup>Dipp</sup> = {CH<sub>2</sub>SiMe<sub>2</sub>NDipp}<sub>2</sub>; Dipp = 2,6-<i>i</i>-Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) reacts with organic azides via reductive N<sub>2</sub> elimination. With the less sterically encumbered azides PhN<sub>3</sub> and C<sub>10</sub>H<sub>15</sub>N<sub>3</sub> (1-azidoadamantane), the putative initially formed aluminium imide undergoes facile [2 + 3] cycloaddition to provide the tetrazenylaluminates [{SiN<sup>Dipp</sup>}Al-κ<i><sup>2</sup>-N</i>,<i>N′</i>-({N(R)}<sub>2</sub>N<sub>2</sub>)]K (R = Ph, C<sub>10</sub>H<sub>15</sub>). In contrast, each Al(I) centre of [{SiN<sup>Dipp</sup>}AlK]<sub>2</sub> only reacts with a single equivalent of 2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>N<sub>3</sub> to provide the imidoaluminate [{SiN<sup>Dipp</sup>}AlN(2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>)(K∙C<sub>6</sub>H<sub>6</sub>)], which crystallises as a monomer and displays a short Al-N distance of 1.7040(13) Å. Attempts to synthesise the azide [{SiN<sup>Dipp</sup>}AlN<sub>3</sub>] by reaction of [{SiN<sup>Dipp</sup>}AlI] with an excess of KN<sub>3</sub> resulted in exclusive formation of the bis(azido)aluminate [{SiN<sup>Dipp</sup>}Al(N<sub>3</sub>)<sub>2</sub>K], which crystallises as an infinite 1-dimensional polymer propagated by μ-(1,3)-N<sub>3</sub> bridging interactions between the potassium cations and azide anions. Although the THF-adducted azide [{SiN<sup>Dipp</sup>}AlN<sub>3</sub>(THF)] may be synthesised and characterised by more stringent control of the reaction stoichiometry, the synthetic viability of this route remains compromised by competitive generation of [{SiN<sup>Dipp</sup>}Al(N<sub>3</sub>)<sub>2</sub>K]. |
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| ISSN: | 2304-6740 |