Disclosed in this communication is a thorough study on the dearomative addition of organomagnesium nucleophiles to N-alkyl pyridinium electrophiles. The regiochemical outcomes have observable and predictable trends associated with the...

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. NH4+/complex after protonolysis, which is a 50% yield based on reducing equivalents. The series of triiron compounds tested evidences the subtle effects of ancillary donors, including halides, hydrides, sulfides, and carbonyl ligands, and metal oxidation state on N(SiMe3)3 yield, and highlight Fe3(μ3-N)L as a common species in product mixtures. These results suggest that ancillary ligands can be abstracted with Lewis acids under reducing conditions.

The triiron trihydride complex Fe3H3 L (1) [where L 3– is a tris(β-diketiminate)cyclophanate] reacts with CO and with BF3·OEt2 to afford (FeICO)2FeII(μ3-H)L (2) and Fe3F3 L (3), respectively.