Abstract Dewar benzenes, the metastable valence isomers of benzenes, have been extensively studied both experimentally and theoretically. In contrast, little is known about Dewar metallabenzenes having a transition metal in the skeletal framework, despite the recent intensive interest in the development of chemistry of metallabenzenes. Herein, we report the isolation and characterization of the first examples of structurally characterized Dewar metallabenzenes. These compounds were generated via unprecedented reactions of metallacyclobutadienes with aminoalkynes.
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