5,5,15,15‐Tetraoxo‐5,15‐Dithiaporphyrin as a Highly Electron‐Deficient Porphyrinic Ligand
5,5,15,15‐Tetraoxo‐5,15‐Dithiaporphyrin as a Highly Electron‐Deficient Porphyrinic Ligand
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5,5,15,15-四氧-5,15-二硫代卟啉作为高度缺电子的卟啉配体
DOI：
10.1002/chem.201903639
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Shinokubo Hiroshi
中科院分区：
文献类型：
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作者：
Yagi Atsumi;Kondo Takeshi;Yamashita Daisuke;Wachi Naruhiko;Omori Hiroto;Fukui Norihito;Ikeue Takahisa;Shinokubo Hiroshi
用间氯苯甲酸氧化5，15-二硫杂卟啉，高产率地合成了相应的S，S-四氧化物。电化学分析和理论计算表明，合成的5，5，15，15-四氧-5，15-二硫杂卟啉具有高度的缺电子性质。四氧二硫杂卟啉与醋酸锌和醋酸镍反应得到了有效的金属络合物。由于缺电子配体增加了金属中心的Lewis酸性，镍配合物在溶液和固体中分别形成五配位和六配位的高自旋(S=1)配合物。吡啶与镍中心的结合常数显著高于传统的卟啉镍配合物。对高自旋NiII络合物的随温度变化的磁化率测量表明，存在弱的铁磁相互作用。
Oxidation of 5,15‐dithiaporphyrin withmeta‐chloroperbenzoic acid afforded the correspondingS,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 NiIIcenter was significantly higher than those of conventional porphyrin NiIIcomplexes. Temperature‐dependent magnetic susceptibility measurements of the high‐spin NiIIcomplex revealed the presence of weak ferromagnetic interactions.