Crystal structures and coordination-site exchange reactions of palladium(II) and platinum(II) complexes containing tris[2-(tert-butylthio)ethyl]amine |
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| Affiliation: | 1. Department of Chemistry, Aichi University of Education, Igaya, Kariya 448-8542, Japan;2. Department of Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan;3. Department of Chemistry, Faculty of Science, Okayama University, Tsushima, Okayama 700-8530, Japan;1. Key Laboratory of Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, China;2. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin, 300072, China;1. State Key Laboratory for Mechanical Behavior of Materials, School of Materials Science and Engineering, Xi''an Jiaotong University, Xi''an, 710049, PR China;2. School of Materials Science and Engineering, Nanyang Technological University, Nanyang Avenue, Singapore;3. Department of Chemistry, School of Science. Xi''an Jiaotong University, Xi''an, 710049, PR China;1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, Hubei, China;2. NRC (Nanostructure Research Centre), Wuhan University of Technology, Wuhan 430070, China;3. College of Science, Wuhan University of Science and Technology, Wuhan, 430081, China;1. Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181, UCCS – Unité de Catalyse et Chimie du Solide, F-59000 Lille, France;2. Laboratoire de Génie des Procédés Catalytiques, LGPC, CNRS, CPE Lyon, Université de Lyon, F-69616 Villeurbanne, France;3. IRCELyon, CNRS-Lyon 1, 2 Avenue Albert Einstein, F-69626 Villeurbanne Cedex, France;4. Univ. Lille, CNRS, UMR 8576, UGSF – Unité de Glycobiologie Structurale et Fonctionnelle, F-59000 Lille, France |
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| Abstract: | Palladium(II) and platinum(II) complexes, [PdX(NS3 1Bu)]BPh4 (X=Cl, Br, I; NS3 1Bu=tris[2-(tert-butylthio)ethyl]amine) and [PtCl(NS3 1Bu)]BPh4, were prepared, and their structures were determined by X-ray analyses. The geometry around the palladium and platinum atoms is square planar. The NS3 1Bu ligand functions as a tridentate ligand and one sulfur atom is not coordinated to the metal. The 1H NMR spectrum of [PdCl(NS3 1Bu)]BPh4 in acetone-d6 exhibited a dynamic behavior. At 20°C the spectrum showed a singlet signal at 1.60 ppm that can be assigned to tert-butyl protons, whereas at −70°C three singlet signals were observed at 1.36, 1.61, and 1.70 ppm with an intensity ratio of 1: 0.25: 2. The signals at 1.36 and 1.70 ppm are assigned to the tert-butyl protons in the square-planar structure, and these signals are consistent with the X-ray structure. The signal at 1.61 ppm can be assigned to the tert-butyl protons in a trigonal-bipyramidal structure where the three tert-butyl groups are magnetically equivalent. Thus, we concluded that the coordination-site exchange occurred via a trigonal-bipyramidal intermediate. The square-planar and trigonal-bipyramidal species of [PdCl(NS3 1Bu)]BPh4 are in equilibrium in acetone-d6. The equilibrium was shifted toward the square-planar species on decreasing the temperature. The 1H NMR spectra for [PdX(NS3 1Bu)]BPh4 (X=Cl, Br, and I) were similar to one another at the same temperature, suggesting that the site-exchange process is insensitive to the kind of coexisting halogen ligand. The site exchange reaction of [PtCl(NS3 1Bu)]BPh4 seems to occur more slowly than that of the palladium(II) analogue. |
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