Iron-catalysed transformation of molecular dinitrogen into silylamine under ambient conditions

Abstract

Although stoichiometric transformations using transition metal–N₂ complexes have been well investigated towards the goal of nitrogen fixation under mild reaction conditions, only a few examples of the catalytic transformations of N₂ using transition metal–N₂ complexes as catalysts have been reported. In almost all the catalytic systems, the use of Mo is essential to realize the catalytic transformation of N₂, where Mo–N₂ complexes are considered to work as effective catalysts. Here we show the first successful example of the Fe-catalysed transformation of N₂ into N(SiMe₃)₃ under ambient conditions, in which iron complexes such as iron pentacarbonyl [Fe(CO)₅] and ferrocenes have been found to work as effective catalysts. A plausible reaction pathway is proposed, where Fe(II)–N₂ complex bearing two Me₃Si groups as ancillary ligands has an important role as a key reactive intermediate, with the aid of density-functional-theory calculations.