Dinitrogen Functionalization Affording Chromium Diazenido and Side-on η-Hydrazido Complexes.

Isolation of key intermediate complexes in dinitrogen functionalization is crucial for elucidating the mechanistic details and further investigation. Herein, the synthesis and characterization of (μ-η:η-N)(η-N)-Cr(I) and (η-N)-Cr(0) complexes supported by Cp* (Cp* = CMe) and NHC ligands were reported. Further functionalization of Cr(0)-N complex with silyl halides delivered the key intermediates in the alternating pathway, the chromium diazenido complex and the chromium side-on η-hydrazido complex . Protonation of led to the quantitative formation of NH. Moreover, the [η-MeSiNNSiMe] unit in enabled N-C bond formation reactions with CO and BuNCO, giving the corresponding ,-chelating hydrazidochromium complexes and , respectively.