A Nickel-Doped Dehydrobenzoannulene-Based Two-Dimensional Covalent Organic Framework for the Reductive Cleavage of Inert Aryl C–S Bonds

The development of metalated covalent organic frameworks (COFs) is useful for generating recyclable catalytic systems for practical applications. Herein, we report the synthesis, characterization, and catalytic properties of an azine-linked two-dimensional (2D) COF containing nickel-doped dehydrobenzoannulene (DBA) units. We demonstrate that Ni-DBA-2D-COF can be used to reductively cleave the aryl C–S bonds of several organosulfur compounds utilizing dimethylethylsilane as the reducing agent. The Ni-DBA-2D-COF catalytic system displays excellent recyclability and good yields. This work highlights a rare example of utilizing metalated DBA complexes to perform catalytic transformations.