Manganese substituted Compound i of cytochrome P450 biomimetics: A comparative reactivity study of MnV-oxo versus MnIV-oxo species

Reza Latifi, Laleh Tahsini, Baharan Karamzadeh, Nasser Safari, Wonwoo Nam, Sam P. De Visser

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Manganese-oxo porphyrins have been well studied as biomimetic models of cytochromes P450 and are known to be able to catalyze substrate hydroxylation reactions. Recent experimental studies [J.Y. Lee, Y.-M. Lee, H. Kotani, W. Nam, S. Fukuzumi, Chem. Commun. (2009) 704] showed that Mn(V)-oxo porphyrins react rapidly with 10-methyl-9,10-dihydroacridine (AcrH2) via a proton-coupled-electron-transfer followed by an electron transfer. In this work, we present a computational study on the reactivity patterns of Mn(V)-oxo and Mn(IV)-oxo with respect to AcrH2. This study shows that although both oxidants are capable of hydroxylating AcrH2, the MnV-oxo species is the more active oxidant. We have generalized these observations with thermodynamic cycles that explain the reaction mechanisms and electron transfer processes. For the MnV-oxo mechanism the reactions proceed with a fast spin state crossing from the ground state singlet to the triplet spin state prior to a hydrogen atom transfer followed by another electron transfer. The present results are fully consistent with previous studies on iron-oxo porphyrins and manganese-oxo porphyrins and shows that the interplay of low lying singlet and triplet spin state surfaces influences the reaction mechanisms and kinetics.

Original languageEnglish
Pages (from-to)4-13
Number of pages10
JournalArchives of Biochemistry and Biophysics
Issue number1
StatePublished - 1 Mar 2011

Bibliographical note

Funding Information:
The National Service of Computational Chemistry Software (NSCCS) is acknowledged for CPU time provided. S.P.D.V. thanks the Royal Society of Chemistry for an RSC Journal Grant. R.L. and L.T. thank the British Council for an Exchange grant. W.N. acknowledges financial support from the NSF/MEST of Korea through the CRI Program and the WCU Program ( R31-2008-000-10010-0 ).


  • Biomimetic
  • Hydride transfer
  • Hydroxylation
  • Iron-oxo
  • Manganese-oxo
  • Porphyrin


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