Metal–Metal Cooperative C─F and S─F Bond Cleavage by Low‐Valent Tetracobalt Clusters and Water‐Assisted Fluoroarene Hydrodefluorination

ABSTRACT We report the self‐assembly of paramagnetic, tetrahedral tetra‐cobalt(I) clusters supported by structurally flexible N‐donor, bipyridine‐based ligand platforms, which are capable of structural rearrangement of their tetrametallic core via small molecule activation. In particular, Co I 4 clusters cleave S─F and C─F bonds in SF 6 and fluoroarenes in the presence of water, resulting in fluoride trapping between two Co atoms in an overall tetrametallic Co II core, while aerobic oxidation of a tetra‐cobalt(I) cluster results in isolation of a Co III oxo‐bridged cubane cluster. Hydrodefluorination of polyfluorinated arenes was achieved using water without the need to utilize silanes or boranes: isotope‐labeling experiments confirmed that the hydrogen in the hydrodefluorinated products originates from water.