A Copper(I) Catenane Decorated Metal–Organic Layer as a Heterogenous Catalyst for Dehydrogenative Cross‐Coupling

Abstract While earth‐abundant metals are green and sustainable alternatives to precious metals for catalytic chemical conversions, the fast ligand exchange involving most of the base metals renders their development into robust, reusable catalysts very challenging. Described in this work is a new type of heterogeneous catalyst derived from a 2D metal‐organic layer (MOL) grafted with catenane‐coordinated Cu(I) complexes. In addition to the good substrate accessibility, easy functionalization, and other favorable features due to the MOL support, the mechanical bond in the anchored catenane ligands also represents a new mechanism to dynamically confine the coordination environment and kinetically stabilize the coordinated Cu(I) to give a well‐defined, active yet stable heterogeneous catalyst. Pilot catalytic studies using a model dehydrogenative C─O cross‐coupling reaction showed that the Cu(I) catenane‐grafted MOL led to exclusive formation of the C─O coupled product, whereas control catalysis using a similar Cu(I) catalyst supported by non‐interlocked macrocyclic ligands was found to also give a C─C coupled by‐product, whose formation was found to be mediated by the uncontrolled oxidation of the Cu(I) to Cu(II), highlighting the distinctive roles and untapped potential of the catenane coordination in developing base metal‐derived catalysts for challenging catalytic conditions.