Journal article
Palladium(II) Chloride Complexes of N,N′-Disubstituted Imidazole-2-thiones: Syntheses, Structures, and Catalytic Performances in Suzuki–Miyaura and Sonogashira Coupling Reactions
Inorganic Chemistry, Vol.56(18), pp.11230-11243
2017
Abstract
Reactions of PdCl2 with 2 equiv of N,N′-disubstituted-imidazole-2-thiones R1R2C3N2S (R1 = R2 = Me (1a), iPr (1b), Cy (1c), C6Me3H2 (1d); R1 = Me, R2 = Ph (1e)) under the different conditions afford five mononuclear complexes trans-[(R1R2C3N2S)2PdCl2] (R1 = R2 = Me (2a), iPr (2b), Cy (2c), C6Me3H2 (2d); R1 = Me, R2 = Ph (2e)) and five binuclear Pd(II) complexes [(PdCl2){μ-(R1R2C3N2S)}]2 (R1 = R2 = Me (3a), iPr (3b), Cy (3c), C6Me3H2 (3d); R1 = Me, R2 = 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.
Details
- Title
- Palladium(II) Chloride Complexes of N,N′-Disubstituted Imidazole-2-thiones: Syntheses, Structures, and Catalytic Performances in Suzuki–Miyaura and Sonogashira Coupling Reactions
- Authors
- Li-Ming Zhang (Author) - Sanchow University, ChinaHai-Yan Li (Author) - Sanchow University, ChinaHong-Xi Li (Author) - Sanchow University, ChinaDavid James Young (Author) - University of the Sunshine Coast - Faculty of Science, Health, Education and EngineeringYong Wang (Author) - Sanchow University, ChinaJian-Ping Lang (Author) - Sanchow University, China
- Publication details
- Inorganic Chemistry, Vol.56(18), pp.11230-11243
- Publisher
- American Chemical Society
- Date published
- 2017
- DOI
- 10.1021/acs.inorgchem.7b01616
- ISSN
- 0020-1669
- Organisation Unit
- University of the Sunshine Coast, Queensland
- Language
- English
- Record Identifier
- 99451138402621
- Output Type
- Journal article
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- Collaboration types
- Domestic collaboration
- International collaboration
- Web Of Science research areas
- Chemistry, Inorganic & Nuclear