| Autor: |
Zhai DD; Department of Chemistry, Fudan University, Shanghai 200438, China., Zhang SQ; Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China., Xie SJ; Department of Chemistry, Fudan University, Shanghai 200438, China., Wu RK; Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China., Liu F; Department of Chemistry, Fudan University, Shanghai 200438, China., Xi ZF; Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China., Hong X; Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China.; Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, School of Science, Westlake University, Hangzhou 310024, China.; Beijing National Laboratory for Molecular Sciences, Zhongguancun North First Street No. 2, Beijing 100190, PR China., Shi ZJ; Department of Chemistry, Fudan University, Shanghai 200438, China. |
| Abstrakt: |
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. |
