Metathetical reactions of alkali–metal derivatives of the dianion [tBuN(Se)P(μ-NtBu)2P(Se)NtBu]2− (2Se2−) with Ag(NHC)Cl, Ag[BF4], AuCl(THT) and HgCl2, as well as the reaction of 2S2− with AuCl(THT) were investigated. The observed products all incorporate the monoprotonated ligands 2SeH− or 2SH− in a variety of structural arrangements around the metal centres, including tetrameric and trimeric macrocycles [Ag and Au (E = Se)], a ladder (Au, E = S) and a spirocycle (Hg); the ladder contains both the dianion 2S2− and the monoanion 2SH− as ligands linking three Au2 units. All complexes have been characterised in the solid state by single crystal X-ray analyses and in solution by multinuclear (1H, 31P and 77Se) NMR spectra.
