Synthesis, Characterization, And Reactivity Of Metalla-Chalcogenirenium Compounds(Dagger)

Main observation and conclusionChalcogenirenium cations, featuring an unsaturated three-membered organic ring, are limited but known to be synthesizable from alkynes with bulky electron-donating groups. Metalla-chalcogenirenium compounds have been synthesized as stable compounds through the reactions of a cyclic metal-carbyne complex-metallapentalyne with PhSCl, PhSeCl or PhTeCl. As a result of the high strain in the three-membered metallacycles, the metalla-chalcogenirenium cations react readily with the base or chloride ions. These reactions furnish a series of unprecedented chalcogenirenium cations with intact M=C bonds. The intrinsic stabilization effect of aromaticity is further elucidated by density functional calculations.