Metallaaromaticity involving a d(0) early transition metal centre: synthesis, structure, and aromaticity of tantallapyridinazirine complexes

Though late transition metal aromatic metallabenzenes and related heteroatom-containing analogues have been well studied, the corresponding aromatic early transition metal complexes remain elusive. Herein, we demonstrate the synthesis of aromatic, planar, and delocalised organotantallapyridinium complexes via a simple one-pot process by sequential treatment of tantalum methyl complex [η(5):σ-Me(2)C(C(5)H(4))(C(2)B(10)H(10))]TaMe(3) with alkynes and isocyanide. Single-crystal X-ray analyses, NMR spectroscopic data and DFT calculations suggest that they are aromatic tantallapyridinium complexes, a class of long-sought-after molecules. This work would shed some light on the preparation of metallaaromatics involving early transition metals.