Dinitrogen Functionalization Affording Chromium Diazenido and Side-on η<sup>2</sup>-Hydrazido Complexes
Zhu‐Bao Yin, Botao Wu, Gao‐Xiang Wang, Junnian Wei, Zhenfeng Xi
Abstract
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 1:η 1 -N 2 )(η 1 -N 2 )-Cr(I) 3 and (η 1 -N 2 ) 2 -Cr(0) complexes 4 supported by Cp* (Cp* = C 5 Me 5 ) and NHC ligands were reported. Further functionalization of Cr(0)-N 2 complex 4 with silyl halides delivered the key intermediates in the alternating pathway, the chromium diazenido complex 5 and the chromium side-on η 2 -hydrazido complex 6 . Protonation of 6 led to the quantitative formation of N 2 H 4 . Moreover, the [η 2 -Me 3 SiNNSiMe 3 ] 2– unit in 6 enabled N–C bond formation reactions with CO 2 and t BuNCO, giving the corresponding N, O -chelating hydrazidochromium complexes 7 and 8, respectively.