Trapping of a Transient Base‐Stabilised Alumylene and Alumylene‐Type Reactivity of a Self‐Stabilising Dialumene towards Organic Azides

Abstract The reduction of a carbene‐coordinated, sterically encumbered terphenyl‐substituted aluminium diiodide, (LRAlI 2 ), yielded a “masked” dialumene (LRAl=AlRL), self‐stabilised through [2+2] cycloaddition with a peripheral aromatic group. During the course of the reaction, a carbene‐stabilised arylalumylene (LRAl:) was generated in situ, which was trapped using an alkyne, generating an aluminacyclopropene or a C−H activated product thereof, depending on the steric bulk of the alkyne. The masked dialumene also underwent intramolecular cycloreversion and dissociation into alumylene fragments, which reacted with various organic azides to yield monomeric or dimeric iminoalanes depending on the sterics of the azide substituent. The thermodynamics of monomeric and dimeric iminoalane formation were probed by theoretical calculations.