Novel development of umpolung at main group element: Synthesis, structure and reactivity of nucleophilic aluminyl anion

Synthesis and characterization of a dimer of an aluminyl anion complex have been achieved by using a xanthene-based bulky tridentate ligand. The fact that this species acts as a nucleophile provides the evidence of umpolung at the central aluminium atoms. In addition, this dimeric species and its monomeric analogs displayed a distinctive reactivity to cause the C-H and C-C oxidative addition of benzene, respectively. Furthermore, the reaction of the monomeric analog with a gold reagent affords an aluminum-gold heteronuclear complex, which exhibits nucleophilic reactivity with the insertion of CO2 at the gold center. © 2019 Society of Synthetic Organic Chemistry. All rights reserved.