Direct Incorporation of Dinitrogen into an Aliphatic C-H Bond.

Autor: 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., Huang YF; Department of Chemistry, Fudan University, Shanghai 200438, China., Chen HL; 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., Liu F; Department of Chemistry, Fudan University, Shanghai 200438, China., Zhai DD; Department of Chemistry, Fudan University, Shanghai 200438, 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.; State Key Laboratory of Organometallic Chemistry, SIOC, CAS, Shanghai 200032, China.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2023 Mar 29; Vol. 145 (12), pp. 6773-6780. Date of Electronic Publication: 2023 Feb 23.
DOI: 10.1021/jacs.2c13086
Abstrakt: The activation of dinitrogen (N 2 ) and direct incorporation of its N atom into C-H bonds to create aliphatic C-N compounds remains unresolved. Incompatible conditions between dinitrogen reduction and C-H functionalization make this process extremely challenging. Herein, we report the first example of dinitrogen insertion into an aliphatic C sp 3 -H bond on the ligand scaffold of a 1,3-propane-bridged [N 2 N] 2- -type dititanium complex. Mechanistic investigations on the behaviors of dinuclear and mononuclear Ti complexes indicated the intramolecular synergistic effect of two Ti centers at a C-N bond-forming step. Computational studies revealed the critical isomerization between the inactive side-on N 2 complex and the active nitridyl complex, which is responsible for the C sp 3 -H amination. This strategy maps an efficient route toward the future synthesis of aliphatic amines directly from N 2 .
Databáze: MEDLINE
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