Self-Assembly of Customizable Nickel Trifluoromethylation Catalysts via Dynamic C‒O and C‒F Bond Activation

Using a combination of metal-promoted reactivity, dynamic covalent chemistry, 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 mul-tiple steps and a tedious and low-yielding separation. This suggest 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.