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<p>Benzene reduction by molecular complexes remains an important synthetic challenge, requiring harsh reaction conditions involving group I metals. Reductions of benzene, to date, typically result in a loss of aromaticity, although the benzene tetra-anion, a 10π-electron system, has been calculated to be stable and aromatic. Due to the lack of sufficiently potent reductants, four-electron reduction of benzene usually requires the use of group I metals. Here we demonstrate the four-electron reduction of benzene and some of its derivatives using a samarium(<span>ii</span>) alkyl reagent, with no requirement for group I metals. Whereas organosamarium(<span>ii</span>) typically reacts through one-electron processes, the compounds reported here feature a rare two-electron process. Combined experimental and computational results implicate a transient samarium(<span>i</span>) intermediate involved in this reduction process, which ultimately provides the benzene tetra-anion. The remarkably strong reducing power of this samarium(<span>ii</span>) alkyl implies a rich reactivity, providing scope for its application as a reducing agent.</p><p></p>

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Four-electron reduction of benzene by a samarium(ii)-alkyl without the addition of external reducing agents

  • 期刊论文

  • 发表日期：

    2025年1月3日

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  • Georgia M. Richardson,
  • Thayalan Rajeshkumar,
  • Finlay M. Burke,
  • Scott A. Cameron,
  • Brooke D. Nicholls,
  • Joanne E. Harvey,
  • Robert A. Keyzers,
  • Tane Butler,
  • Simon Granville,
  • Lujia Liu,
  • Julien Langley,
  • Li F. Lim,
  • Nicholas Cox,
  • Nicholas F. Chilton,
  • Jamie Hicks,
  • Nathaniel J. L. K. Davis,
  • Laurent Maron,
  • Mathew D. Anker

摘要

Benzene reduction by molecular complexes remains an important synthetic challenge, requiring harsh reaction conditions involving group I metals. Reductions of benzene, to date, typically result in a loss of aromaticity, although the benzene tetra-anion, a 10π-electron system, has been calculated to be stable and aromatic. Due to the lack of sufficiently potent reductants, four-electron reduction of benzene usually requires the use of group I metals. Here we demonstrate the four-electron reduction of benzene and some of its derivatives using a samarium(ii) alkyl reagent, with no requirement for group I metals. Whereas organosamarium(ii) typically reacts through one-electron processes, the compounds reported here feature a rare two-electron process. Combined experimental and computational results implicate a transient samarium(i) intermediate involved in this reduction process, which ultimately provides the benzene tetra-anion. The remarkably strong reducing power of this samarium(ii) alkyl implies a rich reactivity, providing scope for its application as a reducing agent.