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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
남원우Shunichi Fukuzumi이용민서미숙
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 이용민scopusscopus; 서미숙scopusscopus
Issue Date
2019
Journal Title
Journal of the American Chemical Society
ISSN
0002-7863JCR Link
Citation
Journal of the American Chemical Society vol. 141, no. 3, pp. 1324 - 1336
Publisher
American Chemical Society
Indexed
SCI; SCIE; SCOPUS WOS 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
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자연과학대학 > 화학·나노과학전공 > Journal papers
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