Self-Assembly of a Customizable Library of Nickel Trifluoromethylation Catalysts via Selective C─F and C─O Bond Cleavage

Using a combination of metal-promoted reactivity, in situ covalent bond modification, and hydrogen bonding-promoted fluorine labilization, a unified approach was developed to self-assemble a library of customizable ligand architectures directly at the nickel center via selective cleavage of C─F or C─O bonds and the formation of C─C or C─N bonds. As a result, a structurally diverse set of nickelacarbatrane and pincer complexes was obtained, including unsymmetrical and mixed-heterocyclic atranes and trifluoromethylated pincers that cannot be accessed by conventional organic synthetic methods or require multiple steps and a tedious and low-yielding separation. This suggests a possibility of a spontaneous generation of high-complexity structures from a commonly used metal precursor and simple N-heterocycle building blocks, despite commonly believed innocence of the C─F bonds, which may also generate catalytically active species.