Ligand K-edge X-ray absorption spectroscopy of [Fe4S4]1+,2+,3+ clusters: changes in bonding and electronic relaxation upon redox

Journal of the American Chemical Society
Abhishek DeyEdward I Solomon

Abstract

Sulfur K-edge X-ray absorption spectroscopy (XAS) is reported for [Fe(4)S(4)](1+,2+,3+) clusters. The results are quantitatively and qualitatively compared with DFT calculations. The change in covalency upon redox in both the [Fe(4)S(4)](1+/2+) (ferredoxin) and the [Fe(4)S(4)](2+/3+) (HiPIP) couple are much larger than that expected from just the change in number of 3d holes. Moreover, the change in the HiPIP couple is higher than that of the ferredoxin couple. These changes in electronic structure are analyzed using DFT calculations in terms of contributions from the nature of the redox active molecular orbital (RAMO) and electronic relaxation. The results indicate that the RAMO of HiPIP has 50% ligand character, and hence, the HiPIP redox couple involves limited electronic relaxation. Alternatively, the RAMO of the ferredoxin couple is metal-based, and the ferredoxin redox couple involves extensive electronic relaxation. The contributions of these RAMO differences to ET processes in the different proteins are discussed.

References

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Citations

May 13, 2005·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Alex H PriemWilfred R Hagen
May 7, 2011·Inorganic Chemistry·Travis V Harris, Robert K Szilagyi
Nov 15, 2011·Inorganic Chemistry·Stephen SproulesKarl Wieghardt
Apr 22, 2009·The Journal of Physical Chemistry. a·Shuqiang Niu, Toshiko Ichiye
Mar 26, 2008·Chemical Society Reviews·Edward I SolomonAbhishek Dey
Feb 18, 2014·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Sunshine C SilverJoan B Broderick
Jul 18, 2008·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Martin G O'TooleCraig A Grapperhaus
Jun 22, 2006·Journal of Computational Chemistry·Robert K Szilagyi, Mark A Winslow
Jan 25, 2014·Journal of Computational Chemistry·Travis V Harris, Robert K Szilagyi
Dec 6, 2017·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Geng DongUlf Ryde
Sep 29, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Partha HalderAtanu Rana
Sep 26, 2020·Journal of the American Chemical Society·Charles H ArnettTheodor Agapie
Jul 19, 2017·Journal of the American Chemical Society·Yang HaEdward I Solomon
Mar 20, 2015·Journal of the American Chemical Society·Sowmya SubramanianMichael K Johnson
Feb 21, 2014·Inorganic Chemistry·Christopher J PollockSerena DeBeer

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