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

Stoichiometric reduction of N-2 at a Mo center stabilized by a bulky tetradentate phosphine ligand (PP3Cy) allowed isolation of Mo-imidoamine and Mo-imido complexes. Both complexes as well as the Mo-II precursor are equally suitable catalysts for the synthesis of NTMS3 (TMS-trimethylsilyl) from N-2, TMSCl, and electron sources. Mechanistic studies prove the involvement of a TMS radical at least in one of the catalytic steps.