Stepwise selective oxidation of tris(2-(diphenylphosphino)ethyl)phosphine on thiolato palladium(II) complexes |
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Authors: | Sen-ichi Aizawa Tatsuya Kawamoto |
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Affiliation: | a Faculty of Engineering, Toyama University, 3190 Gofuku, Toyama 930-8555, Japan b Department of Chemistry, Graduate School of Science, Osaka University, 1-16 Machikaneyama, Toyonaka, Osaka 560-0043, Japan |
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Abstract: | One of the equatorially coordinated terminal phosphorus atoms of tris(2-(diphenylphosphino)ethyl)phosphine (pp3) ligand on the five-coordinate trigonal-bipyramidal palladium(II) complex, [Pd(4-Cltp)(pp3)](BF4) (4-Cltp = 4-chlorothiophenolate), was selectively oxidized by photolysis to form the four-coordinate square-planar complex. Further selective oxidation of another coordinated terminal phosphorus atom proceeded quantitatively by the substitution reaction with 4-chlorothiophenolate. The solid state structures of these stepwise-oxidized square-planar complexes were determined by X-ray crystal structure analyses, and the structures of the starting trigonal-bipyramidal and the oxidized complexes in solution have been characterized by 31P NMR spectroscopy. |
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Keywords: | Stepwise oxidation Tetradentate phosphine ligands Photolysis Thiolato ligands Trigonal-bipyramidal palladium(II) complexes |
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