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Redox Reactivity of a Mononuclear Manganese-Oxo Complex Binding Calcium Ion and Other Redox-Inactive Metal Ions
- Title
- Redox Reactivity of a Mononuclear Manganese-Oxo Complex Binding Calcium Ion and Other Redox-Inactive Metal Ions
- Authors
- Sankaralingam M.; Lee Y.-M.; Pineda-Galvan Y.; Karmalkar D.G.; Seo M.S.; Jeon S.H.; Pushkar Y.; Fukuzumi S.; Nam W.
- Ewha Authors
- 남원우; Shunichi Fukuzumi; 이용민; 서미숙
- SCOPUS Author ID
- 남원우; Shunichi Fukuzumi; 이용민; 서미숙
- Issue Date
- 2019
- Journal Title
- Journal of the American Chemical Society
- ISSN
- 0002-7863
- Citation
- Journal of the American Chemical Society vol. 141, no. 3, pp. 1324 - 1336
- Publisher
- American Chemical Society
- Indexed
- SCIE; SCOPUS
- Document Type
- Article
- Abstract
- Mononuclear nonheme manganese(IV)-oxo complexes binding calcium ion and other redox-inactive metal ions, [(dpaq)MnIV(O)]+-Mn+ (1-Mn+, Mn+ = Ca2+, Mg2+, Zn2+, Lu3+, Y3+, Al3+, and Sc3+) (dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate), were synthesized by reacting a hydroxomanganese(III) complex, [(dpaq)MnIII(OH)]+, with iodosylbenzene (PhIO) in the presence of redox-inactive metal ions (Mn+). The Mn(IV)-oxo complexes were characterized using various spectroscopic techniques. In reactivity studies, we observed contrasting effects of Mn+ on the reactivity of 1-Mn+ in redox reactions such as electron-transfer (ET), oxygen atom transfer (OAT), and hydrogen atom transfer (HAT) reactions. In the OAT and ET reactions, the reactivity order of 1-Mn+, such as 1-Sc3+ ≈ 1-Al3+ > 1-Y3+ > 1-Lu3+ > 1-Zn2+ > 1-Mg2+ > 1-Ca2+, follows the Lewis acidity of Mn+ bound to the Mn-O moiety; that is, the stronger the Lewis acidity of Mn+, the higher the reactivity of 1-Mn+ becomes. In sharp contrast, the reactivity of 1-Mn+ in the HAT reaction was reversed, giving the reactivity order 1-Ca2+ > 1-Mg2+ > 1-Zn2+ > 1-Lu3+> 1-Y3+> 1-Al3+ ≈ 1-Sc3+ that is, the higher is Lewis acidity of Mn+, the lower the reactivity of 1-Mn+ in the HAT reaction. The latter result implies that the Lewis acidity of Mn+ bound to the Mn-O moiety can modulate the basicity of the metal-oxo moiety, thus influencing the HAT reactivity of 1-Mn+ cytochrome P450 utilizes the axial thiolate ligand to increase the basicity of the iron-oxo moiety, which enhances the reactivity of compound I in C-H bond activation reactions. © 2018 American Chemical Society.
- DOI
- 10.1021/jacs.8b11492
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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