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

Abstract

Carbon dioxide (CO2) is a potent greenhouse gas of growing environmental concern. Seeking to offer a solution to the so‐called “CO2‐problem”, the chemistry community have turned a focus toward transition metal complexes, which can activate, reduce, and convert CO­2 into carbon‐based products. As a poignant design element, metal‐ligand cooperativity (MLC), 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” brand 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 conversion selectivity. In the laboratory, chemists can test hypothesis and concepts, and can rationalize why a given pairing of transition metal/Lewis‐acid lead to specific CO2 reduction outcomes. This concept piece identifies specific 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 impact.