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 ( ${{\rm PP}{{{\rm Cy}\hfill \atop 3\hfill}}}$) 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 N₂, TMSCl, and electron sources. Mechanistic studies prove the involvement of a TMS radical at least in one of the catalytic steps. [ABSTRACT FROM AUTHOR]