Conversion of N2 into oxadiazoles promoted by a multinuclear samarium complex
Xianghui Shi1, Qiong Yuan1, Yuanjin Chen1
1Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, China.
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The nitrogenous compounds play a substantial role in life. Transformation of N2 into high-value nitrogen-containing organic compounds, not through NH3, is of great significance but poses a long-standing challenge. Compared with d-block metals, the derivatization chemistry of rare-earth metal dinitrogen complexes remains elusive. Here we report the single-electron reductions of tetrametallic samarium dinitrogen complex 1 [L4Sm4N2(THF)2] (L = [(CH2)5C(C4H3N)2]2-) in THF with dipyrrolide dianion as the ligand, to obtain ionic complexes 2 and 3, [L4Sm4N2]M(THF)6 (M = K, Na), respectively. Different from 2, 3 could dissolve in Et2O to give complex 4 [L4Sm4N2Na(Et2O)], featuring a side-on coordination of Na to dinitrogen molecule. When upon extended reaction time, a more nucleophilic complex 5 [L4Sm3N2Na3] is achieved. Moreover, further reaction of 5 with many aroyl chlorides to successfully afford corresponding oxadiazole organic compounds from N2, facilitated by rare-earth metal [(N2)4-] unit.
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