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Probing the structural effects on the intrinsic electronic and redox properties of [2Fe–2S]+ clusters, a broken-symmetry density functional theory study

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Abstract

In biological electron transport chains, [2Fe–2S] clusters have versatile electrochemical properties and serve as important electron carriers in a wide variety of biological processes. To understand structural effects on the variation in reduction potentials in [2Fe–2S] proteins, a series of [2Fe–2S] protein analogs with bidentate ligands ( − SC 2 H 4 NH 2) were recently produced by collision-induced dissociation of [Fe 4 S 4(L)4]2− (L  =  SC 2 H 4 NH 2). Combined with photoelectron spectroscopy findings, the reaction mechanisms of [Fe 4 S 4(L)4]2− to [Fe 2 S 2(L)2]− and the structural effects of ligands on the electronic and redox properties of the [2Fe–2S] clusters are investigated here using broken-symmetry density functional theory method. Our calculations suggest that [Fe 2 S 2(η2 − L)(cis − L)]− and [Fe 2 S 2(η2 − L)2]− are the experimentally observed [2Fe–2S] products, which are generated via a fission process of [Fe 4 S 4(L)4]2− followed by rearrangement of ligands of [Fe 2 S 2(L)2]−. Moreover, structural variation of the ferrous center may dramatically affect the oxidation energy of the [2Fe–2S] clusters.

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Authors and Affiliations

  1. Department of Chemistry, Georgetown University, Washington, DC, 20057-1227, USA

    Shuqiang Niu & Toshiko Ichiye

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  1. Shuqiang Niu
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  2. Toshiko Ichiye
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Correspondence to Toshiko Ichiye.

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Niu, S., Ichiye, T. Probing the structural effects on the intrinsic electronic and redox properties of [2Fe–2S]+ clusters, a broken-symmetry density functional theory study. Theor Chem Acc 117, 275–281 (2007). https://doi.org/10.1007/s00214-006-0136-y

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