Tetrazenyl-, Imido-, and Azidoaluminate Derivatives of a Sterically Demanding Bis-silazide Ligand

Han-Ying Liu, Ryan J. Schwamm, Jakub Kenar, Mary F. Mahon, Michael S> Hill

Research output: Contribution to journalArticlepeer-review

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 languageEnglish
Article number25
JournalInorganics
Volume13
Issue number1
Early online date16 Jan 2025
DOIs
Publication statusPublished - 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

Fingerprint

Dive into the research topics of 'Tetrazenyl-, Imido-, and Azidoaluminate Derivatives of a Sterically Demanding Bis-silazide Ligand'. Together they form a unique fingerprint.

Cite this