Synthesis and Characterization of Cyclopropaosmanaphthalenes Containing a Fused σ-Aromatic Metallacyclopropene Unit

Metalla-aromatics are important complexes that show unique properties owing to their highly conjugated systems, which show Hückel or Möbius aromaticity. Recently, several metalla-aromatics showing spiro-aromaticity or σ-aromaticity have been reported. Herein, we report the isolation of the first cyclopropametallanaphthalenes, in which the metallacyclopropene ring shows σ-aromaticity and weak hyperconjugative aromaticity. The reaction of OsCl₂ (PPh₃ )₃ with o-ethynylphenyl alkynes in the presence of PPh₃ followed by protonation with HCl yielded the first cyclopropametallanaphthalenes. The reaction mechanism and the aromaticity were also investigated by density functional theory studies.