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Smallest acyclic tricationic molecule containing a Bis(phosphine)-stabilized low-valent triantimony-based Unit
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Smallest acyclic tricationic molecule containing a Bis(phosphine)-stabilized low-valent triantimony-based Unit
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Journal Article
Smallest acyclic tricationic molecule containing a Bis(phosphine)-stabilized low-valent triantimony-based Unit
2026
Overview
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 = CF
3
SO
3
) possesses reactive polar Sb
δ+
–O
δ–
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.
Element-element bonded multiply charged cationic species are well known as dimers or small cyclic oligomers in the condensed phase but the smallest acyclic version, a trinuclear unit possessing greater than a monocationic charge, has remained elusive. Here the authors report a bis(phosphine) supported low valent triantimony-based tricationic compound.
