A series of trinuclear and dinuclear Cr(I)-N-2 complexes bearing cyclopentadienyl-phosphine ligands were synthesized and characterized. Further reduction of the Cr(I)-N-2 complexes generated anionic Cr(0)-N-2 complexes, which could react with Me3SiCl to afford the first chromium hydrazido complex from N-2 functionalization. These complexes were found to be effective catalysts for the transformation of N-2 into N(SiMe3)(3).