Catalytic Dinitrogen Reduction at the Molybdenum Center Promoted by a Bulky Tetradentate Phosphine Ligand

Stoichiometric reduction of N2 at a Mo center stabilized by a bulky tetradentate phosphine ligand (PP Cy 3 ) allowed isolation of Mo–imidoamine and Mo–imido complexes. Both complexes as well as the MoII precursor are equally suitable catalysts for the synthesis of NTMS3 (TMS=trimethylsilyl) from N2, TMSCl, and electron sources. Mechanistic studies prove the involvement of a TMS radical at least in one of the catalytic steps.