TY - JOUR
T1 - Stable Iron Porphyrin Intramolecularly Coordinated by Alcoholate Anion
T2 - Synthesis and Evaluation of Axial Ligand Effect of Alcoholate on Spectroscopy and Catalytic Activity
AU - Shirakawa, Yoshinori
AU - Yano, Yuuki
AU - Niwa, Yuki
AU - Inabe, Kanako
AU - Umezawa, Naoki
AU - Kato, Nobuki
AU - Hisamatsu, Yosuke
AU - Higuchi, Tsunehiko
N1 - Funding Information:
*E-mail: higuchi@phar.nagoya-cu.ac.jp. ORCID Naoki Umezawa: 0000-0003-3966-2303 Tsunehiko Higuchi: 0000-0002-3586-4680 Present Address N. Kato: Graduate School of Science, Tohoku University, 6-3, Aoba, Aramaki, Aoba-ku, Sendai 980-8578, Japan. Author Contributions All authors contributed to writing the manuscript. All authors have given approval to the final version of the manuscript. Funding This work was supported in part by Grants-in-Aid for Scientific Research (A) (No. 20249006) from the Japan Society for the Promotion of Science (JSPS). We are also grateful for support by the Platform Project for Supporting Drug Discovery and Life Science Research (No. 12760016, No. 16am0101055j-0005) from MEXT, and by the Japan Agency for Medical Research and Development (AMED). Notes The authors declare no competing financial interest.
Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/4/1
Y1 - 2019/4/1
N2 - 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 to 1a and 1b was 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, SR complex, was much higher than that of 1a. ©
AB - 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 to 1a and 1b was 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, SR complex, was much higher than that of 1a. ©
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U2 - 10.1021/acs.inorgchem.8b03384
DO - 10.1021/acs.inorgchem.8b03384
M3 - Article
C2 - 30896162
AN - SCOPUS:85063386269
VL - 58
SP - 4268
EP - 4274
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 7
ER -