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<p>The nitrogenous compounds play a substantial role in life. Transformation of N<sub>2</sub> into high-value nitrogen-containing organic compounds, not through NH<sub>3</sub>, is of great significance but poses a long-standing challenge. Compared with <i>d</i>-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 <b>1</b> [L<sub>4</sub>Sm<sub>4</sub>N<sub>2</sub>(THF)<sub>2</sub>] (L = [(CH<sub>2</sub>)<sub>5</sub>C(C<sub>4</sub>H<sub>3</sub>N)<sub>2</sub>]<sup>2-</sup>) in THF with dipyrrolide dianion as the ligand, to obtain ionic complexes <b>2</b> and <b>3</b>, [L<sub>4</sub>Sm<sub>4</sub>N<sub>2</sub>]M(THF)<sub>6</sub> (M = K, Na), respectively. Different from <b>2</b>, <b>3</b> could dissolve in Et<sub>2</sub>O to give complex <b>4</b> [L<sub>4</sub>Sm<sub>4</sub>N<sub>2</sub>Na(Et<sub>2</sub>O)], featuring a side-on coordination of Na to dinitrogen molecule. When upon extended reaction time, a more nucleophilic complex <b>5</b> [L<sub>4</sub>Sm<sub>3</sub>N<sub>2</sub>Na<sub>3</sub>] is achieved. Moreover, further reaction of <b>5</b> with many aroyl chlorides to successfully afford corresponding oxadiazole organic compounds from N<sub>2</sub>, facilitated by rare-earth metal [(N<sub>2</sub>)<sup>4-</sup>] unit.</p>

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Conversion of N2 into oxadiazoles promoted by a multinuclear samarium complex

  • 期刊论文

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  • 发表日期：

    2025年12月12日

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  • Xianghui Shi,
  • Qiong Yuan,
  • Yuanjin Chen,
  • Zhenfeng Xi,
  • Junnian Wei

摘要

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.