Herein, we report a novel method for the synthesis of metallabenzenes by swapping the phosphorus atom in an aromatic phosphinine ring with transition metal fragments. The oxidation of a phosphine-phosphinine-phosphine pincer iridium complex by O triggered the replacement of the phosphorus atom of the phosphinine ring by an iridium fragment to afford iridabenzene. Dianionic rhodabenzene was also synthesized from a phosphinine rhodium complex by oxidation of the phosphorus atom, followed by subsequent reduction using metallic potassium. The aromaticity of the newly synthesized irida- and rhoda-benzenes was evaluated both experimentally and theoretically.
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