(n‑Bu) 4 NBr-promoted N 2 splitting to molybdenum nitride Dandan Zhai 2 , Zhang-jie Shi 1 , Shuo-Qing Zhang 2 , Si-Jun Xie 1 , Rong-Kai Wu 2 , Feng Liu 1 , Zhen-Feng Xi 3 , Xin Hong 2,4,5 1 Fudan University, China, 2 Zhejiang University, China, 3 Peking University, China, 4 Westlake University, China Splitting of N 2 via six-electron reduction and further functionalization to value-added products is one of the most important and challenging chemical transformations in N 2 fixation. However, most N 2 splitting approaches rely on strong chemical or electrochemical reduction to generate highly reactive metal species to bind and activate N 2 , which is often incompatible with functionalizing agents. Catalytic and sustainable N 2 splitting to produce metal nitrides under mild conditions may create efficient and straightforward methods for N-containing organic compounds. Herein, we present that a readily available and nonredox (n-Bu) 4 NBr can promote N 2 -splitting with a Mo(III) platform. Both experimental and theoretical mechanistic studies suggest that simple X − (X = Br, Cl, etc.) anions could induce the disproportionation of Mo III [N(TMS)Ar] 3 at the early stage of the catalysis to generate a catalytically active {Mo II [N(TMS)Ar] 3 } − species. The quintet Mo II species prove to be more favorable for N 2 fixation kinetically and thermodynamically, compared with the quartet Mo III counterpart. Especially, computational studies reveal a distinct heterovalent {Mo II −N 2 −Mo III } dimeric intermediate for the N≡N triple bond cleavage. References 1. Forrest, S. J. K.; Schluschaß, B.; Yuzik-Klimova, E. Y.; Schneider, S. Nitrogen Fixation via Splitting into Nitrido Complexes. Chem. Rev. 2021 , 121 , 6522−6587. 2. 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. 3. Zhai, D.; Zhang, S.; Xie, S,; Wu, R,; Liu, F.; Xi, Z.; Hong, X.; Shi, Z-J.( n ‑Bu) 4 NBr-Promoted N 2 Splitting to Molybdenum Nitride. J. Am. Chem. Soc. 2022 , 144 , 14071−14078.
P51
© The Author(s), 2023
Made with FlippingBook Learn more on our blog