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

Abstract

Abstract 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.