Cobalt-catalyzed transformation of molecular dinitrogen into silylamine under ambient reaction conditions.

The first successful example of cobalt-catalyzed reduction of N2 with Me3 SiCl and Na as a reductant, under ambient reaction conditions, gives N(SiMe3 )3 , which can be readily converted into NH3 . In this reaction system, 2,2'-bipyridine (bpy) is found to work as an effective additive to improve substantially the catalytic activity. CoN2 complexes bearing three Me3 Si groups as ancillary ligands are considered to work as key reactive species based on DFT calculations. The DFT results also allow the proposal of a detailed reaction pathway for the transformation of N2 into N(SiMe3 )3 .

Iron-catalyzed aromatic amination for nonsymmetrical triarylamine synthesis.

Novel iron-catalyzed amination reactions of various aryl bromides have been developed for the synthesis of diaryl- and triarylamines. The key to the success of this protocol is the use of in situ generated magnesium amides in the presence of a lithium halide, which dramatically increases the product yield. The present method is simple and free of precious and expensive metals and ligands, thus providing a facile route to triarylamines, a recurrent core unit in organic electronic materials as well as pharmaceuticals.