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<p>The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis and characterization of a highly reduced bismuth salt featuring a cationic core based on three contiguous Bi(I) centres. The triatomic bismuth-based core exhibits an electronic configuration that mimics the canonical description of the archetypical carbon-based <i>π</i>-allyl cation. Structural, spectroscopic and theoretical analyses validate the unique <i>π</i>-delocalization between the bismuth’s highly diffused 6<i>p</i> orbitals, resulting in a bonding situation in which the three bismuth atoms are interconnected by two bonds, formally possessing a 1.5 bond order each. This electronic situation defines this complex as the heaviest and stable <i>π</i>-allyl cation of the periodic table. Furthermore, we demonstrate that the newly synthesized complex is able to act as a synthon for the transfer of a Bi(I) cation to forge other low-valent organobismuth complexes.</p><p></p>

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A trimetallic bismuth(I)-based allyl cation

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年1月6日

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  • Davide Spinnato,
  • Nils Nöthling,
  • Markus Leutzsch,
  • Maurice van Gastel,
  • Lucas Wagner,
  • Frank Neese,
  • Josep Cornella

摘要

The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis and characterization of a highly reduced bismuth salt featuring a cationic core based on three contiguous Bi(I) centres. The triatomic bismuth-based core exhibits an electronic configuration that mimics the canonical description of the archetypical carbon-based π-allyl cation. Structural, spectroscopic and theoretical analyses validate the unique π-delocalization between the bismuth’s highly diffused 6p orbitals, resulting in a bonding situation in which the three bismuth atoms are interconnected by two bonds, formally possessing a 1.5 bond order each. This electronic situation defines this complex as the heaviest and stable π-allyl cation of the periodic table. Furthermore, we demonstrate that the newly synthesized complex is able to act as a synthon for the transfer of a Bi(I) cation to forge other low-valent organobismuth complexes.