Molecular Switching through Chalcogen-Bond-Induced Isomerization of Binuclear (Diaminocarbene)PdII Complexes

Binuclear diaminocarbene complexes, which form as a regioisomer mixture in the reaction between isocyanide–palladium(II) complex cis-[PdCl2(CNXyl)2] and 1,3-thiazol-2-amine, are able to exchange an anionic chloride ligand with other halides, such Br or I. This process also affords binuclear complexes mixtures of kinetically thermodynamically controlled regioisomers. In CDCl3 solutions, we observed interconversion The results DFT calculations revealed that CHCl3 solution, each pair isomers exhibited two different types chalcogen bonding S···X S···N; presence CBs for solid state was proven through X-ray crystallographic study. Based on combined experimental theoretical data, it could be concluded thermodynamic favorability formation regioisomers increases Cl < ≈ I row correlate well energy difference S···N (X = Cl, Br, I) bonds products. means is possible change structure metallocycles by simply replacing one halide another.