Stepwise phosphine sulfide formation and metal-bridging reaction of tetradentate and tridentate phosphine ligands on palladium(II) |
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Authors: | Sen-ichi Aizawa Tatsuya Kawamoto Chie Ishimura |
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Affiliation: | a Graduate School of Science and Engineering, University of Toyama, 3190 Gofuku, Toyama 930-8555, Japan b Department of Chemistry, Faculty of Science, Kanagawa University, Hiratsuka, Kanagawa 259-1293, Japan |
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Abstract: | Kinetic studies on the stepwise phosphine sulfide formation reaction of the five-coordinate trigonal-bipyramidal Pd(II) complexes with the tripodal tetradentate phosphine ligand, [PdCl(pp3)]Cl and [Pd(4-Cltp)(pp3)](BF4) (pp3 = tris[2-(diphenylphosphino)ethyl]phosphine; 4-Cltp = 4-chlorothiophenolate), were carried out, and it was revealed that the reactions proceeded via the intermediate with a pendant dissociated phosphino group. Formation of the intermediate was utilized for the bridging reaction onto Pt(II) to form the phosphine-bridged linear trinuclear and cyclic tetranuclear mixed-metal complexes. Difference in the steric conversion mechanism in the phosphine-bridging reaction between the linear tridentate phosphine (bis[2-(diphenylphosphino)ethyl]phenylphosphine) and pp3 is also reported. |
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Keywords: | Kinetics Phosphine sulfide formation Phosphine-bridging reaction Steric conversion mechanism |
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