Reduction vs. Addition: The Reaction of an Aluminyl Anion with 1,3,5,7‐Cyclooctatetraene

Abstract

The potassium aluminyl complex K[Al(NON^Ar )] (NON=NON^Ar =[O(SiMe₂ NAr)₂ ]^2- , Ar=2,6-iPr₂ C₆ H₃ ) reacts with 1,3,5,7-cyclooctatetraene (COT) to give K[Al(NON^Ar )(COT)]. The COT-ligand is present in the asymmetric unit as a planar μ₂ -η² :η⁸ -bridge between Al and K, with additional K⋅⋅⋅π-aryl interactions to neighboring molecules that generate a helical chain. DFT calculations indicate significant aromatic character, consistent with reduction to [COT]^2- . Addition of 18-crown-6 causes a rearrangement of the C₈ -carbocycle to form the isomeric 9-aluminabicyclo[4.2.1]nona-2,4,7-triene anion.