Axial ligand orientations in a distorted porphyrin macrocycle: synthesis, structure, and properties of low-spin bis(imidazole)iron(III) and iron(II) porphyrinates

Inorganic Chemistry
Ranjan PatraSankar Prasad Rath

Abstract

We have reported here, for the first time, the parallel and perpendicular orientation preferences of two planar and unhindered imidazoles as axial ligands (L) while coordinated toward iron(III) and iron(II) porphyrins, respectively, in a nonplanar porphyrinic environment. The synthesis and characterization of low-spin Fe(III)(tn-OEP)(L)(2) x ClO(4) and Fe(II)(tn-OEP)(L)(2) are reported. Fe(III)(tn-OEP)(L)(2) x ClO(4) shows rhombic electron paramagnetic resonance (EPR) spectra (at 77 K) in both solid and solution phases that are very characteristic for low-spin (S = 1/2) iron porphyrins with two axial imidazole ligands aligned parallel to each other. Single-point energy calculation is also performed on Fe(III)(tn-OEP)(1-MeIm)(2)(+) using density functional theory (DFT), which shows that the relative parallel orientations of two 1-MeIm are more stable than the perpendicular orientations. X-ray structures of Fe(II)(tn-OEP)(1-MeIm)(2) and Fe(II)(tn-OEP)(1-MeIm)(2).THF are reported that demonstrate, for the first time, the near-perpendicular axial ligand orientation (80.9 and 89.8 degrees, respectively) for iron(II) porphyrins in a distorted macrocyclic environment. Even starting from parallel axial orientations of 1-MeIm, geometry ...Continue Reading

References

May 1, 1987·Proceedings of the National Academy of Sciences of the United States of America·Z X XiaF S Mathews
Mar 22, 1972·Journal of the American Chemical Society·D M CollinsJ L Hoard
Feb 17, 1983·Biochimica Et Biophysica Acta·A L T'sai, G Palmer
Jan 5, 1984·Journal of Molecular Biology·Y HiguchiM Kakudo
Apr 9, 1998·Biophysical Journal·W JentzenJ A Shelnutt
Dec 18, 2003·Journal of the American Chemical Society·Liliya A YatsunykF Ann Walker
Mar 3, 2005·Chemical Communications : Chem Comm·Ru-Jen ChengChih-Ching Chang
Jun 7, 2005·Inorganic Chemistry·Chuanjiang HuW Robert Scheidt
Jan 5, 2006·Chemical Communications : Chem Comm·Mathias O Senge
Apr 18, 2008·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Edward A Berry, F Ann Walker
May 2, 2008·Acta Crystallographica. Section E, Structure Reports Online·Nathan J SilvernailW Robert Scheidt

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Citations

Jun 2, 2011·Chemical & Pharmaceutical Bulletin·Mingyu JiaoTadao Ishizuka
Jun 16, 2016·Chemistry : a European Journal·Debangsu SilSankar Prasad Rath
Jan 6, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Firoz Shah Tuglak KhanSankar Prasad Rath
Jul 7, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Baiyin HeJianfeng Li
Jul 15, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Debangsu Sil, Sankar Prasad Rath
Apr 18, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Firoz Shah Tuglak KhanSankar Prasad Rath
Jun 11, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Amit KumarSankar Prasad Rath
Aug 25, 2016·Chemistry : a European Journal·Debangsu SilSankar Prasad Rath
Feb 14, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·M A FuchsM Döring
Mar 31, 2021·Proceedings of the National Academy of Sciences of the United States of America·Megan L ShelbyLin X Chen
Aug 24, 2017·The Journal of Physical Chemistry. a·Thai T H TranYuhlong O Su
Aug 28, 2018·Inorganic Chemistry·Firoz Shah Tuglak KhanSankar Prasad Rath

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