A Constraining and Redox-Active Aluminum Species With Diverse Reactivity.

This work reports the synthesis, full characterization, and multifaceted reactivity of a highly reactive aluminum complex (2·Et2O) supported by a sterically hindered, redox-active pincer ligand. Characterization by X-ray crystallography and spectroscopic methods confirmed its molecular structure, while Gutmann-Beckett studies and calculated fluoride ion affinity quantified its significant Lewis acidity. The reactivity profile of 2·Et2O is remarkably diverse: it undergoes facile photoinduced species formation, activates the O─H bond via metal-ligand cooperative heterolytic cleavage, and engages in redox reactions with substrates such as Ph3CCl and PhSSPh. Most notably, 2·Et2O demonstrates distinct selectivity in activating the C─I bond of iodoalkanes. This process proceeds via a kinetically favored or cooperative pathway, leading to alkyl group transfer to the ligand, rather than the thermodynamically preferred σ-bond oxidative addition at the aluminum center. This study highlights how the synergy between an Al(III) center and a non-innocent pincer ligand can unlock unique reaction manifolds, expanding the potential of main-group elements in stoichiometric bond activation.

• Publication year

  2026

• Venue

  Angewandte Chemie

• Publication date

  2026-02-17

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1002/anie.202524691PMID 41700085
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar

• No claims are published for this paper.

• No concepts are published for this paper.

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