Craig‐Hückel Hybrid Aromatic Metalla‐dehydroannulenes Constructed by a Formal Cycloaddition Reaction

Aromatic metalla‐annulenes are important aromatic compounds, research into which has been mainly concentrated on metal‐benzenes and their lower homologues. Reports on their superior homologs are rare, and this has greatly limited the systematic study of their properties. In this work, a series of osma‐dehydro[11]annulenes with good air and thermal stability were prepared in high yields through a simple [10+1] strategy, by incorporating a metal fragment into conjugated ten‐carbon chains in a one‐pot reaction. They are the first monometallic aromatic metalla‐[n]annulenes with the ring size larger than 6, and their Craig‐Hückel hybrid aromaticity is supported by various physical and computational parameters. Besides, these complexes show versatile reactivities, not only giving further evidence for their aromaticity, but also demonstrating their physical and chemical properties can easily be regulated. This work enriches the metalla‐aromatic chemistry, and provides a new avenue for the synthesis of large metalla‐annulenes with different ring sizes.