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Donor-Stabilized Antimony(I) and Bismuth(I) Ions: Heavier Valence Isoelectronic Analogues of Carbones
journal contribution
posted on 2021-01-12, 17:40 authored by Mujahuddin
M. Siddiqui, Samir Kumar Sarkar, Mohd Nazish, Massimiliano Morganti, Christian Köhler, Jiali Cai, Lili Zhao, Regine Herbst-Irmer, Dietmar Stalke, Gernot Frenking, Herbert W. RoeskyIsolation
of two-coordinate compounds of heavier Group 15 elements
in low oxidation state is challenging due to the preferential formation
of dimers or oligomers. Herein, we report the first examples of donor-stabilized
two-coordinate Sb(I) and Bi(I) ions. The reduction of antimony and
bismuth trihalides with KC8 in the presence of cyclic alkyl(amino)
carbene (cAAC) afforded Sb(I) and Bi(I) cations in the form of triflate
salts [(cAAC)2Sb][OTf] (1) and [(cAAC)2Bi][OTf] (2). Compounds 1 and 2 belong to a new class of acyclic cations of Group 15 with
eight valence electrons and are heavier valence isoelectronic analogues
of carbones. Both compounds are isolated and well-characterized by
NMR spectroscopy, cyclic voltammetry, single-crystal X-ray diffraction,
and computational studies.
