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Palladium(II) Chloride Complexes of N,N'-Disubstituted Imidazole-2-thiones: Syntheses, Structures, and Catalytic Performances in Suzuki-Miyaura and Sonogashira Coupling Reactions.

Research paper by Li-Ming LM Zhang, Hai-Yan HY Li, Hong-Xi HX Li, David James DJ Young, Yong Y Wang, Jian-Ping JP Lang

Indexed on: 26 Aug '17Published on: 26 Aug '17Published in: Inorganic Chemistry



Abstract

Reactions of PdCl2 with 2 equiv of N,N'-disubstituted-imidazole-2-thiones R(1)R(2)C3N2S (R(1) = R(2) = Me (1a), (i)Pr (1b), Cy (1c), C6Me3H2 (1d); R(1) = Me, R(2) = Ph (1e)) under the different conditions afford five mononuclear complexes trans-[(R(1)R(2)C3N2S)2PdCl2] (R(1) = R(2) = Me (2a), (i)Pr (2b), Cy (2c), C6Me3H2 (2d); R(1) = Me, R(2) = Ph (2e)) and five binuclear Pd(II) complexes [(PdCl2){μ-(R(1)R(2)C3N2S)}]2 (R(1) = R(2) = Me (3a), (i)Pr (3b), Cy (3c), C6Me3H2 (3d); R(1) = Me, R(2) = Ph (3e)), respectively. Complexes 2a-2e are easily converted into the corresponding 3a-3e by adding equimolar PdCl2 in refluxing MeOH, while the reverse reaction is achieved at room temperature by addition of 2 equiv of 1a-1e. In 2b, 2d, and 2e, each Pd(II) holds a distorted square planar geometry completed by two trans Cl atoms and two trans S atoms. Complexes 3a-3e have a dimeric [Pd2S2] structure in which two {PdCl2} units are interlinked by two N,N'-disubstituted-imidazole-2-thiones. Each Pd(II) adopts a distorted square planar geometry accomplished by two cis Cl atoms and two cis bridging S atoms. Among them, complex 3d has the two largest C6Me3H2 groups on the 2 and 5 positions of imidazole-2-thione, the longest Pd-μ-S bond, the largest S-Pd-S angle, and displays the highest catalytic activity toward Suzuki-Miyaura and copper-free Sonogashira cross-coupling reactions, which are confirmed by density functional theory calculations. The results provide an interesting insight into the introduction of various substituent groups into the periphery ligands of coordination complex-based catalysts, which could tune their geometric structures to acquire the best catalytic activity toward organic reactions.