In Situ Formation of Frustrated Lewis Pairs in a Water‐Tolerant Metal‐Organic Framework for the Transformation of CO2

Frustrated Lewis pairs (FLPs) consist of sterically hindered Lewis acids and Lewis bases, which provide high catalytic activity towards non‐metal‐mediated activation of “inert” small molecules, including CO2 among others. One critical issue of homogeneous FLPs, however, is their instability upon recycling, leading to catalytic deactivation. Herein, we provide a solution to this issue by incorporating a bulky Lewis acid‐functionalized ligand into a water‐tolerant metal‐organic framework (MOF), named SION‐105, and employing Lewis basic diamine substrates for the in situ formation of FLPs within the MOF. Using CO2 as a C1‐feedstock, this combination allows for the efficient transformation of a variety of diamine substrates into benzimidazoles. SION‐105 can be easily recycled by washing with MeOH and reused multiple times without losing its identity and catalytic activity, highlighting the advantage of the MOF approach in FLP chemistry. Frustriert, aber produktiv: Ein auf Bor basierendes, in Wasser stabiles metallorganisches Gerüst agiert als heterogener Katalysator in der Umwandlung von CO2 und setzt dabei frustrierte Lewis‐Paare ein. Mit CO2 als C1‐Rohstoff wurde eine Vielzahl an Diamin‐Substraten in wertvolle Benzimidazole umgewandelt.