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Abstract
The potassium alumanyl [{SiN Dipp}AlK] 2 (SiN Dipp = {CH 2SiMe 2NDipp} 2; Dipp = 2,6-i-Pr 2C 6H 3) reacts with organic azides via reductive N 2 elimination. With the less sterically encumbered azides PhN 3 and C 10H 15N 3 (1-azidoadamantane), the putative initially formed aluminium imide undergoes facile [2 + 3] cycloaddition to provide the tetrazenylaluminates [{SiN Dipp}Al-κ 2-N,N′-({N(R)} 2N 2)]K (R = Ph, C 10H 15). In contrast, each Al(I) centre of [{SiN Dipp}AlK] 2 only reacts with a single equivalent of 2,4,6-Me 3C 6H 2N 3 to provide the imidoaluminate [{SiN Dipp}AlN(2,4,6-Me 3C 6H 2)(K∙C 6H 6)], which crystallises as a monomer and displays a short Al-N distance of 1.7040(13) Å. Attempts to synthesise the azide [{SiN Dipp}AlN 3] by reaction of [{SiN Dipp}AlI] with an excess of KN 3 resulted in exclusive formation of the bis(azido)aluminate [{SiN Dipp}Al(N 3) 2K], which crystallises as an infinite 1-dimensional polymer propagated by μ-(1,3)-N 3 bridging interactions between the potassium cations and azide anions. Although the THF-adducted azide [{SiN Dipp}AlN 3(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 Dipp}Al(N 3) 2K].
Original language | English |
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Article number | 25 |
Journal | Inorganics |
Volume | 13 |
Issue number | 1 |
Early online date | 16 Jan 2025 |
DOIs | |
Publication status | Published - 31 Jan 2025 |
Data Availability Statement
NMR spectra and crystal data are given in the Supplementary Materials. Crystal data and details of the data collection and refinement are given in Table S1. Crystallographic data for 1–5 have been deposited with the Cambridge Crystallographic Data Centre (CCDC 2369737–2369741). Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: +44-1223-336033; email: [email protected] or http://www.ccdc.cam.ac.uk).Funding
We thank the Royal Commission for the Exhibition of 1851 for the provision of a Postdoctoral Fellowship (R.J.S.).
Keywords
- Al(I)
- azide
- imide
- tetrazene
ASJC Scopus subject areas
- Inorganic Chemistry
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Dive into the research topics of 'Tetrazenyl-, Imido-, and Azidoaluminate Derivatives of a Sterically Demanding Bis-silazide Ligand'. Together they form a unique fingerprint.Projects
- 1 Finished
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Ryan Schwamm- 1851 Fellowship - Activation of Nitrogen using Alkaline Earth Metals
Schwamm, R. (PI) & Hill, M. (CoI)
Royal Commission for the Exhibition of 1851
5/11/18 → 4/11/21
Project: UK charity