Mixed NHC–thiolato complexes of palladium: understanding the formation of di-versus mononuclear complexes

Abstract

The preference for the formation of mono- versus dinuclear mixed carbene/thiolato complexes of Pd^II has been studied with three types of N-heterocyclic carbenes derived from benzimidazole, imidazole and 1,2,4-triazole. The complexes were prepared by treatment of halido/NHC precursors with sodium isopropylthiolate in a salt metathesis reaction. Mononuclear complexes are formed when the sulfur and carbon donors are exclusively cis to each other, while their trans arrangement preferably leads to dinuclear complexes with μ₂-bridging thiolato ligands. The increased electron density in the latter case cannot be sufficiently compensated by one Pd^II center alone and leads to the formation dinuclear species with bridging thiolato ligands.