A Blueprint for Secondary Coordination Sphere Editing: Approaches Toward Lewis‐Acid Assisted Carbon Dioxide Co‐Activation

Carbon dioxide (CO2) is a potent greenhouse gas of environmental concern. Seeking to offer a solution to the “CO2‐problem”, the chemistry community has turned a focus toward transition metal complexes which can activate, reduce, and convert CO2 into carbon‐based products. The design of such systems involves judicious selection of both metal and accompanying donor ligand; in part, these efforts are motivated by biological metalloenzymes that undertake similar transformations. As a design element, metal‐ligand cooperativity, which leverages intramolecular interactions between a transition metal and an adjacent secondary ligand site, has been acknowledged as a vitally important component by the CO2 activation community. These systems offer a “push‐pull” style of activation where electron density is chaperoned onto CO2 with an accompanying electrophile, such as a Lewis‐acid, playing the role of acceptor. This pairing allows for the stabilization of reactive CxHyOz‐containing intermediates and can bias CO2 product selectivity. In the laboratory, chemists can test hypotheses and ideas, enabling rationalization of why a given pairing of transition metal/Lewis‐acid leads to selective CO2 reduction outcomes. This Concept identifies literature examples and highlights key design properties, allowing interested contributors to design, create, and implement novel systems for productive transformations of a small molecule (CO2) with huge potential impact. The reduction of carbon dioxide (CO2) to value‐added products is top‐of‐mind. In this arena, chemists are well‐positioned to lead the charge. Herein, we present advances made in homogeneous CO2 reduction using transition metal/Lewis‐acid systems, with a focus on installing Lewis‐acids into the primary or secondary coordination sphere of the ligand framework.