Spirocyclic, macrocyclic and ladder complexes of coinage metals and mercury with dichalcogeno P2N2-supported anions

Abstract

Metathetical reactions of alkali–metal derivatives of the dianion [^tBuN(Se)P(μ-N^tBu)₂P(Se)N^tBu]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.