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Issue 36, 2017
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The pKa value of the proximal water molecule trans to a high-valent MnV[double bond, length as m-dash]O porphyrin: towards the control of reactivity by pH

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Abstract

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

Graphical abstract: The pKa value of the proximal water molecule trans to a high-valent MnV [[double bond, length as m-dash]] O porphyrin: towards the control of reactivity by pH

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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., 2017,46, 12088-12094
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    The pKa value of the proximal water molecule trans to a high-valent MnV[double bond, length as m-dash]O porphyrin: towards the control of reactivity by pH

    L. Saint-Germes, L. Bar, J. Dejeu, N. Spinelli, E. Defrancq and G. Pratviel, Dalton Trans., 2017, 46, 12088
    DOI: 10.1039/C7DT01829K

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