(n-Bu)4NBr-Promoted N2 Splitting to Molybdenum NitrideClick to copy article linkArticle link copied!
- Dan-Dan Zhai
- Shuo-Qing ZhangShuo-Qing ZhangCenter of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, ChinaMore by Shuo-Qing Zhang
- Si-Jun Xie
- Rong-Kai WuRong-Kai WuCenter of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, ChinaMore by Rong-Kai Wu
- Feng Liu
- Zhen-Feng XiZhen-Feng XiBeijing 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, ChinaMore by Zhen-Feng Xi
- Xin Hong*Xin Hong*Email: [email protected]Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, ChinaKey Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, School of Science, Westlake University, Hangzhou 310024, ChinaBeijing National Laboratory for Molecular Sciences, Zhongguancun North First Street No. 2, Beijing 100190, PR ChinaMore by Xin Hong
- Zhang-Jie Shi*Zhang-Jie Shi*Email: [email protected]Department of Chemistry, Fudan University, Shanghai 200438, ChinaMore by Zhang-Jie Shi
Abstract
Splitting of N2 via six-electron reduction and further functionalization to value-added products is one of the most important and challenging chemical transformations in N2 fixation. However, most N2 splitting approaches rely on strong chemical or electrochemical reduction to generate highly reactive metal species to bind and activate N2, which is often incompatible with functionalizing agents. Catalytic and sustainable N2 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)4NBr can promote N2-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 MoIII[N(TMS)Ar]3 at the early stage of the catalysis to generate a catalytically active {MoII[N(TMS)Ar]3}− species. The quintet MoII species prove to be more favorable for N2 fixation kinetically and thermodynamically, compared with the quartet MoIII counterpart. Especially, computational studies reveal a distinct heterovalent {MoII–N2–MoIII} dimeric intermediate for the N≡N triple bond cleavage.
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