研究室工作进展Feb. 23rd, 2023

Dinitrogen Functionalization Affording Chromium Diazenido and Side-on η2-Hydrazido Complexes

Zhu-Bao Yin, Botao Wu, Gao-Xiang Wang, Junnian Wei*, Zhenfeng Xi*

J. Am. Chem. Soc., 2023. DOI: 10.1021/jacs.3c00266.

 

 

  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-η1:η1-N2)(η1-N2)-Cr(I) 3 and (η1-N2)2-Cr(0) complexes 4 supported by Cp* (Cp* = C5Me5) and NHC ligands were reported. Further functionalization of Cr(0)-N2 complex 4 with silyl halides delivered the key intermediates in the alternating pathway, the chromium diazenido complex 5 and the chromium side-on η2-hydrazido complex 6. Protonation of 6 led to the quantitative formation of N2H4. Moreover, the [η2-Me3SiNNSiMe3]2– unit in 6 enabled N–C bond formation reactions with CO2 and tBuNCO, giving the corresponding N,O-chelating hydrazidochromium complexes 7 and 8, respectively.