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Communication

Electronic Structure and Intrinsic Redox Properties of [2Fe−2S]⁺ Clusters with Tri- and Tetracoordinate Iron Sites

Supporting Info

You-Jun Fu,^†^‡ Shuqiang Niu,^§ Toshiko Ichiye,^§ and Lai-Sheng Wang*^†^‡

Department of Physics, Washington State University, 2710 University Drive, Richland, Washington 99352, W. R. Wiley Environmental Molecular Sciences Laboratory and Chemical Science Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, and Department of Chemistry, Georgetown University, Washington, D.C. 20057-1227

Inorg. Chem., 2005, 44 (5), pp 1202–1204

DOI: 10.1021/ic048559d

Publication Date (Web): February 5, 2005

†

Washington State University.

‡

Pacific Northwest National Laboratory.

Georgetown University.

To whom correspondence should be addressed. E-mail: ls.wang@ pnl.gov.

Abstract

Using potentially bidentate ligands (−SC₂H₄NH₂), we produced [2Fe−2S]⁺ species of different coordination geometries by fission of [4Fe−4S]²⁺ complexes. Even though the ligands are monodentate in the cubane complexes, both mono- and bidentate complexes were observed in the [2Fe] fission products through self-assembly because of the high reactivity of the tricoordinate iron sites. The electronic structure of the [2Fe] species was probed using photoelectron spectroscopy and density functional calculations. It was found that tetracoordination significantly decreases the electron binding energies of the [2Fe] complexes, thus increasing the reducing capability of the [2Fe−2S]⁺ clusters.

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