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Updated: Feb 17, 2026
Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Heavy Group 15 Element Pacman Complexes
Pascal Schmidt1, Liesa Eickhoff2, Karsten Paul Lüdtke1
1Institut für Chemie, Universität Rostock, Albert-Einstein-Straße 3a, D-18059 Rostock, Germany.
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Calix[4]pyrrole macrocycles (Pacman ligands) were used to incorporate heavy pnictogens (As, Sb, and Bi), yielding halogeno-pnictogen complexes (Pac(EX)2, E = As, Sb, Bi; X = Cl, I). Arsenic(III) chloro complex Pac(AsCl)2 was synthesized in solution and isolated, while arsenic(III), antimony(III), and bismuth(III) complexes (Pac(AsI)2, Pac(SbCl)2, Pac(BiCl)2, Pac(BiI)2) were formed in solution but could not be isolated. The arsenic(III) chloro complex showed temperature- and chloride-dependent dynamics similar to Pac(PCl)2. Hydrolysis of transient iodoarsane and chlorostibane produced oxygen-bridged complexes of the type Pac(E-O-E). In the case of the synthesis of Pac(SbCl)2, an intermediate, PacH2(SbCl2)2, was isolated and fully characterized. Through further HCl elimination, the last two HCl molecules were finally split off, resulting in the formation of Pac(SbCl)2. Bismuth(III) analogues were detected only transiently via 1H NMR spectroscopy. All isolated compounds were characterized spectroscopically, crystallographically, and theoretically. Reducing Pac(EX)2 complexes led to decomposition and not to the desired formation of biradical Pac(E·)2.
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