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The pKa value of the proximal water molecule trans to a high-valent MnV=O porphyrin: towards the control of the reactivity by the pH

Abstract

High-valent manganese-oxo species of Mn-TMPyP4 porphyrin interacts in the minor groove of AT-rich regions of DNA and mediates hydroxylation of a C-H bond of deoxyribose leading to DNA break. The reaction was followed at different pH. It is shown that hydroxylation was not efficient at low pH (pH 6) while it worked at higher pH (pH 8). Deprotonation of the coordinated water molecule, trans to the manganese-oxo entity, into a hydroxyl anion drives high-valent manganese-oxo porphyrin toward hydroxylation at pH > 7.

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Publication details

The article was received on 19 May 2017, accepted on 10 Aug 2017 and first published on 10 Aug 2017


Article type: Paper
DOI: 10.1039/C7DT01829K
Citation: Dalton Trans., 2017, Accepted Manuscript
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    The pKa value of the proximal water molecule trans to a high-valent MnV=O porphyrin: towards the control of the reactivity by the pH

    L. Saint-Germes, L. Bar, J. Dejeu, N. Spinelli, E. Defrancq and G. Pratviel, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT01829K

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