The Noninnocence of a 1,2‐Phenylene‐Bridged Bis( <i>β</i> ‐Diketiminate) Ligand

Reduction of a dinuclear aluminum(III) diiodide complex based on a 1,2‐phenylene‐bridged bis( β ‐diketiminate) using sodium on sodium chloride does not afford the expected bimetallic aluminum(I) complex. Instead, an unusual CC coupling between the β ‐carbon atoms of both β ‐diketiminate units takes place and affords a dinuclear aluminum(III) iodide complex with a fused tetracyclic ring system. The new polycyclic complex has been characterized by single‐crystal X‐ray diffraction analysis and nuclear magnetic resonance (NMR) spectroscopy. The reaction is an example of a new type of redox noninnocence of a ( β ‐diketiminate) that enables the synthesis of a new type of ligand.