Efficient Catalytic Conversion of Dinitrogen to N(SiMe₃)₃ Using a Homogeneous Mononuclear Cobalt Complex

Incorporation of the tridentate phosphine-enamidoiminophosphorane onto cobalt­(II) produces tetrahedral Co­(NpNP^iPr)­Cl, <b>1</b>, which upon reduction under dinitrogen generates the T-shaped, paramagnetic Co­(I) complex Co­(NpNP^iPr), <b>2</b>. This paramagnetic T-shaped derivative is in equilibrium with the paramagnetic dinitrogen derivative Co­(NpNP^iPr)­(N₂), <b>3</b>, which can be detected by IR and low-temperature UV–vis spectroscopy. Both <b>1</b> and <b>2</b> act as homogeneous catalysts for the conversion of molecular nitrogen into tris­(trimethylsilyl)­amine (N­(SiMe₃)₃) (∼200 equiv, quantified as NH₄Cl after hydrolysis) in the presence of excess KC₈ and Me₃SiCl at low temperatures