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Selective Conversion of CO 2 into Isocyanate by Low‐Coordinate Iron Complexes
Author(s) -
Broere Daniël L. J.,
Mercado Brandon Q.,
Holland Patrick L.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201802357
Subject(s) - isocyanate , chemistry , selectivity , trimethylsilyl , reaction mechanism , reaction conditions , photochemistry , combinatorial chemistry , polymer chemistry , medicinal chemistry , organic chemistry , catalysis , polyurethane
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.

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