Selective Conversion of CO2 into Isocyanate by Low‐Coordinate Iron Complexes

Discovery of the mechanisms for selective transformations of CO₂ into organic compounds is a challenge. Herein, we describe the reaction of low‐coordinate Fe silylamide complexes with CO₂ to give trimethylsilyl isocyanate and the corresponding Fe siloxide complex. Kinetic studies show that this is a two‐stage reaction, and the presence of a single equivalent of THF influences the rates of both steps. Isolation of a thermally unstable intermediate provides mechanistic insight that explains both the effect of THF in this reaction, and the way in which the reaction achieves high selectivity for isocyanate formation.