Selective Conversion of CO2 into Isocyanate by Low‐Coordinate Iron Complexes. Issue 22 (30th April 2018)

• Record Type: Journal Article
• Authors: Broere, Daniël L. J.; Mercado, Brandon Q.; Holland, Patrick L.
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 22(2018)
• Page Start: 6507
• Page End: 6511
• Publication Date: 2018-04-30
• Subjects: carbon dioxide fixation -- intermediate isolation -- iron -- isocyanate -- low-coordinate complexes; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201802357
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : Carba‐mating with CO2 : Low‐coordinate Fe silylamide complexes react with CO2 to selectively give trimethylsilyl isocyanate and an Fe siloxide complex. Kinetic studies and isolation of a thermally unstable carbamate intermediate provides mechanistic insight that explains the selectivity and the drastic effect that a single equivalent of THF has on this reaction.