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<p>Element-element bonded multiply charged cationic species are well known as dimers or small cyclic oligomers in the condensed phase. However, the smallest acyclic version, a trinuclear unit possessing greater than a monocationic charge, has remained elusive. Here we introduce a bis(phosphine) supported low valent triantimony-based tricationic compound as a new entrant in this field. Structural elucidation and electronic understanding reveal a W-shaped tricationic unit comprising of a three-center four-electron sigma-bonded triantimony moiety that is terminally capped by bis(phosphine) ligands, with the central antimony atom having two lone pairs of electrons. The unique counter trianion [Sb(O)<sub>2</sub>(OTf)<sub>4</sub>]<sup>3–</sup> (OTf = CF<sub>3</sub>SO<sub>3</sub>) possesses reactive polar Sb<sup>δ+</sup>–O<sup>δ–</sup> bonds, the structure of which is determined from single crystal X-ray diffraction analysis. The ensemble of reactive molecular fragments found in this highly charged antimony-based compound makes it thermally unstable. Nonetheless, this fully characterized fleeting species shows a diverse reactivity profile, advancing the isolation of various novel antimony compounds, including the formation of a distinct low-valent antimony-cobalt carbonyl cluster.</p>

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Smallest acyclic tricationic molecule containing a Bis(phosphine)-stabilized low-valent triantimony-based Unit

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年3月21日

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  • Nilanjana Mukherjee,
  • Benjamin Peerless,
  • Vincent L. Nadurata,
  • Vikas Kumar,
  • Mayur P. Sangole,
  • Kirandeep Singh,
  • Haakon T. A. Wiedemann,
  • Christopher W. M. Kay,
  • Robert Kruk,
  • Florian Weigend,
  • Stefanie Dehnen,
  • Rajesh G. Gonnade,
  • Cem B. Yildiz,
  • Moumita Majumdar

摘要

Element-element bonded multiply charged cationic species are well known as dimers or small cyclic oligomers in the condensed phase. However, the smallest acyclic version, a trinuclear unit possessing greater than a monocationic charge, has remained elusive. Here we introduce a bis(phosphine) supported low valent triantimony-based tricationic compound as a new entrant in this field. Structural elucidation and electronic understanding reveal a W-shaped tricationic unit comprising of a three-center four-electron sigma-bonded triantimony moiety that is terminally capped by bis(phosphine) ligands, with the central antimony atom having two lone pairs of electrons. The unique counter trianion [Sb(O)2(OTf)4]3– (OTf = CF3SO3) possesses reactive polar Sbδ+–Oδ– bonds, the structure of which is determined from single crystal X-ray diffraction analysis. The ensemble of reactive molecular fragments found in this highly charged antimony-based compound makes it thermally unstable. Nonetheless, this fully characterized fleeting species shows a diverse reactivity profile, advancing the isolation of various novel antimony compounds, including the formation of a distinct low-valent antimony-cobalt carbonyl cluster.