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Catalytic Silylation of Dinitrogen by a Family of Triiron Complexes

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posted on 09.07.2018, 17:36 by Ricardo B. Ferreira, Brian J. Cook, Brian J. Knight, Vincent J. Catalano, Ricardo García-Serres, Leslie J. Murray
A series of triiron complexes supported by a tris­(β-diketiminate)­cyclophane (L3–) catalyze the reduction of dinitrogen to tris­(trimethylsilyl)­amine using KC8 and Me3SiCl. Employing Fe3Br3L affords 83 ± 7 equiv of NH4+/complex after protonolysis, which is a 50% yield, based on reducing equivalents. The series of triiron compounds tested evidence the subtle effects of ancillary donors, including halides, hydrides, sulfides, and carbonyl ligands, and metal oxidation state on N­(SiMe3)3 yield, and highlight Fe33-N)L as a common species in product mixtures. These results suggest that ancillary ligands can be abstracted with Lewis acids under reducing conditions.