Abstract
Discovery of the mechanisms for selective transformations of CO(2) into organic compounds is a challenge. Herein, we describe the reaction of low-coordinate Fe silylamide complexes with CO(2) 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.