The preference for the formation of mono- dinuclear mixed carbene/thiolato complexes of Pd 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 to each other, while their arrangement preferably leads to dinuclear complexes with μ-bridging thiolato ligands. The increased electron density in the latter case cannot be sufficiently compensated by one Pd center alone and leads to the formation dinuclear species with bridging thiolato ligands.
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