Redox-Neutral Transformations of Carbon Dioxide Using Coordinatively Unsaturated Late Metal Silyl Amide Complexes

Two-coordinate silylamido complexes of nickel and copper rapidly react with CO₂ to selectively form a new cyanate ligand along with hexamethyldisiloxane byproducts. Mechanistic insight into these reactions was obtained from the synthesis of proposed intermediates, several silyl- and phenyl- substituted amido analogues, and their subsequent reactivity with CO₂. These studies suggest that a unique intramolecular double silyl transfer step facilitates CO₂ deoxygenation, which likely contributes to the rapid rates of reaction. The deoxygenation reactions create a platform for a synthetic cycle in which copper amido complexes convert CO₂ to organic silylcarbamates.