02220nas a2200289 4500008004100000245011500041210006900156260000800225300000900233490000700242520124100249100002501490700002301515700002601538700001701564700002301581700002101604700002901625700002801654700001701682700002101699700002101720700002401741700002001765700002201785856012301807 2026 eng d00aSmallest acyclic tricationic molecule containing a Bis(phosphine)-stabilized low-valent triantimony-based Unit0 aSmallest acyclic tricationic molecule containing a Bisphosphines cMAR a26970 v173 a

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 Sb delta+-O delta- 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.

1 aMukherjee, Nilanjana1 aPeerless, Benjamin1 aNadurata, Vincent, L.1 aKumar, Vikas1 aSangole, Mayur, P.1 aSingh, Kirandeep1 aWiedemann, Haakon, T. A.1 aKay, Christopher, W. M.1 aKruk, Robert1 aWeigend, Florian1 aDehnen, Stefanie1 aGonnade, Rajesh, G.1 aYildiz, Cem, B.1 aMajumdar, Moumita uhttps://library.ncl.res.in/content/smallest-acyclic-tricationic-molecule-containing-bisphosphine-stabilized-low-valent