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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2025-01-01
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| author | Han-Ying Liu Ryan J. Schwamm Jakub Kenar Mary F. Mahon Michael S. Hill |
| author_facet | Han-Ying Liu Ryan J. Schwamm Jakub Kenar Mary F. Mahon Michael S. Hill |
| author_sort | Han-Ying Liu |
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| description | 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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| spelling | doaj-art-26cfc36b5680469e8f2734be4d8322a92025-01-24T13:35:31ZengMDPI AGInorganics2304-67402025-01-011312510.3390/inorganics13010025Tetrazenyl-, Imido-, and Azidoaluminate Derivatives of a Sterically Demanding Bis-Silazide LigandHan-Ying Liu0Ryan J. Schwamm1Jakub Kenar2Mary F. Mahon3Michael S. Hill4Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UKDepartment of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UKDepartment of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UKDepartment of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UKDepartment of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UKThe 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].https://www.mdpi.com/2304-6740/13/1/25Al(I)azideimidetetrazene |
| spellingShingle | Han-Ying Liu Ryan J. Schwamm Jakub Kenar Mary F. Mahon Michael S. Hill Tetrazenyl-, Imido-, and Azidoaluminate Derivatives of a Sterically Demanding Bis-Silazide Ligand Inorganics Al(I) azide imide tetrazene |
| title | Tetrazenyl-, Imido-, and Azidoaluminate Derivatives of a Sterically Demanding Bis-Silazide Ligand |
| title_full | Tetrazenyl-, Imido-, and Azidoaluminate Derivatives of a Sterically Demanding Bis-Silazide Ligand |
| title_fullStr | Tetrazenyl-, Imido-, and Azidoaluminate Derivatives of a Sterically Demanding Bis-Silazide Ligand |
| title_full_unstemmed | Tetrazenyl-, Imido-, and Azidoaluminate Derivatives of a Sterically Demanding Bis-Silazide Ligand |
| title_short | Tetrazenyl-, Imido-, and Azidoaluminate Derivatives of a Sterically Demanding Bis-Silazide Ligand |
| title_sort | tetrazenyl imido and azidoaluminate derivatives of a sterically demanding bis silazide ligand |
| topic | Al(I) azide imide tetrazene |
| url | https://www.mdpi.com/2304-6740/13/1/25 |
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