Dinitrogen functionalization affording chromium diazenido and side-on ƞ2-hydrazido complexes Yin Zhu-Bao , Botao Wu, Gao-Xiang Wang, Junnian Wei, Zhenfeng Xi Peking University, China 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 - ƞ 1 : ƞ 1 -N 2 )( ƞ 1 -N 2 )-Cr(I) 3 and ( ƞ 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 ƞ 2 -hydrazido complex 6 . Protonation of 6 led to the quantitative formation of N 2 H 4 . Moreover, the [ ƞ 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. References 1. Chalkley, M. J.; Drover, M. W.; Peters, J. C. Catalytic N 2 -to-NH 3 (or -N 2 H 4 ) Conversion by Well-Defined Molecular Coordination Complexes. Chem . Rev . 2020 , 120 , 5582-5636. 2. Kim, S.; Loose, F.; Chirik, P. J. Beyond Ammonia: Nitrogen–Element Bond Forming Reactions with Coordinated Dinitrogen. Chem . Rev . 2020 , 120 , 5637-5681. 3. Lv, Z.-J.; Wei, J.; Zhang, W.-X.; Chen, P.; Deng, D.; Shi, Z.-J.; Xi, Z. Direct Transformation of Dinitrogen: Synthesis of N-containing Organic Compounds via N−C Bond Formation. Natl . Sci . Rev . 2020 , 7 , 1564-1583.
4. Lv, Z.-J.; Huang, Z.; Zhang, W.-X.; Xi, Z. Scandium-Promoted Direct Conversion of Dinitrogen into Hydrazine Derivatives via N–C Bond Formation. J . Am . Chem . Soc . 2019 , 141 , 8773-8777. 5. Yin, J.; Li, J.; Wang, G.-X.; Yin, Z.-B.; Zhang, W.-X.; Xi, Z. Dinitrogen Functionalization Affording Chromium Hydrazido Complex. J . Am . Chem . Soc . 2019 , 141 , 4241-4247. 6. Gao, Y.; Li, G.; Deng, L. Bis(dinitrogen)cobalt(−1) Complexes with NHC Ligation: Synthesis, Characterization, and Their Dinitrogen Functionalization Reactions Affording Side-on Bound Diazene Complexes. J . Am . Chem . Soc . 2018 , 140 , 2239- 2250. 7. Yin, Z.-B.; Wu, B.; Wang, G.-X.; Wei, J.; Xi, Z. Dinitrogen Functionalization Affording Chromium Diazenido and Side-on ƞ 2 - Hydrazido Complexes.
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