Spectroscopy and electronic structures of mono- and binuclear high-valent non-heme iron-oxo systems

Journal of Inorganic Biochemistry
Andrea DeckerEdward I Solomon

Abstract

High-valent iron-oxo intermediates are known or believed to be key oxidizing species in the catalytic mechanisms of many mononuclear and binuclear non-heme iron enzymes. So far only limited experimental data on their electronic structures are available. In this study we extend knowledge from the experimentally well characterized mononuclear Fe(IV)=O (S=1) biomimetic model system to computational insight into the spectroscopy and electronic structures of mono-and binuclear high-valent iron-oxo enzyme intermediates. In the mononuclear Fe(IV)=O complexes, we predict the spectroscopy and energies of the electronic transitions to be very different for the S=1 and S=2 spin states, but the iron-oxo bonding for both spin states to be very similar. A comparison of the S=2 mono- and binuclear high-valent iron-sites predicts similar electronic transitions. However, the bent iron-oxo bridge and interactions with the second iron-center in the dimer shift the transitions to higher energies and splits the d(xz/yz) orbital set. These electronic structure and TD-DFT results provide a basis for understanding the spectroscopy and electronic structures of high-valent intermediates in mono- and binuclear non-heme iron enzymes.

References

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Feb 19, 2005·Angewandte Chemie·Andrea Decker, Edward I Solomon

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Citations

Sep 28, 2006·Proceedings of the National Academy of Sciences of the United States of America·Lee M HoffartCarsten Krebs
Dec 7, 2007·Journal of the American Chemical Society·Andrea DeckerEdward I Solomon
Aug 21, 2008·Journal of the American Chemical Society·Timothy A JacksonLawrence Que
Jun 20, 2012·Journal of the American Chemical Society·Samuel A WilsonEdward I Solomon
Mar 13, 2009·Current Opinion in Chemical Biology·Edward I SolomonMarina S Chow
Aug 22, 2012·Proceedings of the National Academy of Sciences of the United States of America·Martin SrnecEdward I Solomon
Mar 5, 2014·Chemical Reviews·Edward I SolomonLi Tian
Jul 18, 2017·European Journal of Inorganic Chemistry·Hannah E ColmerJoshua Telser
Jul 15, 2006·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Abhik Ghosh
Apr 3, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Stefania TanaseJan Reedijk
Jun 21, 2008·Chemistry : a European Journal·Feyissa Gadissa GelalchaMatthias Beller
Nov 17, 2009·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Yi Wang, Keli Han
Dec 14, 2006·Physical Chemistry Chemical Physics : PCCP·Manuel J Louwerse, Evert Jan Baerends
Feb 22, 2012·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Arindam MukherjeePeter J Sadler
Nov 22, 2013·Chemical Communications : Chem Comm·Sam P de VisserUlf Ryde
Jun 10, 2014·Chemistry, an Asian Journal·Lining LuChengqi Yi

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