5,5,15,15-Tetraoxo-5,15-Dithiaporphyrin as a Highly Electron-Deficient Porphyrinic Ligand |
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| Authors: | Atsumi Yagi Takeshi Kondo Daisuke Yamashita Naruhiko Wachi Hiroto Omori Dr. Norihito Fukui Prof. Dr. Takahisa Ikeue Prof. Dr. Hiroshi Shinokubo |
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| Affiliation: | 1. Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603 Japan These authors contributed equally to this work.;2. Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603 Japan;3. Department of Chemistry, Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue, 690-8540 Japan |
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| Abstract: | Oxidation of 5,15-dithiaporphyrin with meta-chloroperbenzoic acid afforded the corresponding S,S-tetraoxide in good yield. The resultant 5,5,15,15-tetraoxo-5,15-dithiaporphyrin exhibited the highly electron-deficient nature as elucidated by the electrochemical analysis and theoretical calculations. Treatment of tetraoxodithiaporphyrin with zinc(II) acetate and nickel(II) acetate provided the corresponding metal complexes efficiently. Owing to its enhanced Lewis acidity of the metal center by the electron-deficient ligand, the nickel complex underwent facile axial ligation to form pentacoordinate and hexacoordinate high-spin (S=1) complexes in solution and solid, respectively. The binding constant of pyridine to the NiII center was significantly higher than those of conventional porphyrin NiII complexes. Temperature-dependent magnetic susceptibility measurements of the high-spin NiII complex revealed the presence of weak ferromagnetic interactions. |
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| Keywords: | Lewis acids ligands magnetism porphyrinoids sulfones |
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