Divergent Reactivity of an Isolable Nickelacyclobutane

Nickelacyclobutanes are mostly invoked as reactive intermediates in the reaction of nickel carbenes and olefins to yield cyclopropanes. Nevertheless, early work suggested that other decomposition routes such as β‐hydride elimination and even metathesis could be accessible. Herein, we report the isolation and characterization of a stable pentacoordinated nickelacyclobutane incorporated in a pincer complex. The coordination of different coligands to the nickelacyclobutane determines its selective decomposition along cyclopropanation, metathesis or apparent β‐hydride elimination pathways. DFT calculations shed light on the mechanism of these different pathways. A pincer scaffold allows the isolation of a nickelacyclobutane and a detailed study of its reactivity. The cycle slowly undergoes an apparent beta‐elimination reaction in non‐polar solvents; exposure to additional ligands leads to selective ring cleavage along either the cyclopropanation or the olefin metathesis pathway. These results give insight into the divergent reactivity of metallacyclobutane intermediates.