Stable Iron Porphyrin Intramolecularly Coordinated by Alcoholate Anion: Synthesis and Evaluation of Axial Ligand Effect of Alcoholate on Spectroscopy and Catalytic Activity
Stable Iron Porphyrin Intramolecularly Coordinated by Alcoholate Anion: Synthesis and Evaluation of Axial Ligand Effect of Alcoholate on Spectroscopy and Catalytic Activity
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醇盐阴离子分子内配位的稳定铁卟啉：醇盐轴向配体的合成及评价对光谱和催化活性的影响
DOI：
10.1021/acs.inorgchem.8b03384
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发表时间：
2019
影响因子：
4.6
通讯作者：
Yosuke Hisamatsu and Tsunehiko Higuchi
中科院分区：
文献类型：
--
作者：
Yoshinori Shirakawa;Yuuki Yano;Yuki Niwa;Kanako Inabe;Naoki Umezawa;Nobuki Kato;Yosuke Hisamatsu and Tsunehiko Higuchi
我们合成了分子内脂肪族醇-配位铁卟啉（1a,1b），在另一配体或氧化剂存在下保持其轴向配位。醇类化合物的电子给性低于硫酸盐，第六配体与1和1b的配位能力远低于硫酸盐配位化合物。密度泛函理论计算表明，配位能力的显著差异可以用热力学和空间因素来解释。硫代酸配位化合物sr络合物的催化氧化能力远高于1a。
We synthesized intramolecularly aliphatic alcoholate-coordinated iron porphyrins (1a,1b) that retain their axial coordination in the presence of another ligand or oxidant. The electron-donative character of alcoholate was less than that of thiolate, and the coordination ability of a sixth ligand to1aand1bwas very much lower than in the case of the thiolate-coordinated compounds. Density functional theory calculations indicated that the marked difference in coordination ability could be explained in terms of thermodynamic and steric factors. The catalytic oxidizing ability of the thiolate-coordinated compound,SRcomplex, was much higher than that of1a.