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Spin-state-dependent oxygen sensitivity of iron dithiolates: sulfur oxygenation or disulfide formation

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Abstract

The oxygen sensitivity of two related iron(III) dithiolate complexes of the ligand [4,7-bis-(2′-methyl-2′-mercatopropyl)-1-thia-4,7-diazacyclononane], (bmmp-TASN)FeCN (1) and (bmmp-TASN)FeCl (2), has been examined. Oxygen exposure of the low-spin complex 1 yields the disulfonate complex (bmmp-O6-TASN)FeCN (3) as an olive-green solid with characteristic peaks in the IR spectrum at 1262, 1221, 1111, 1021, 947, 800, and 477 cm−1. The corresponding nickel dithiolate, (bmmp-TASN)Ni (4), yields the related disulfonato derivative, (bmmp-O6-TASN)Ni (5) upon addition of H2O2 (IR bands at 1258, 1143, 1106, 1012, 800, and 694 cm−1. Oxygen exposure of the high-spin complex 2 results in disulfide formation and decomplexation of the metal with subsequent iron-oxo cluster formation. Complexes 1 and 2 were examined using density functional theory calculations. A natural bond order/natural localized molecular orbital covalency analysis reveals that the low-spin complex 1 contains Fe–Sthiolate bonds with calculated covalencies of 75 and 86%, while the high-spin complex 2 contains Fe–Sthiolate bonds with calculated covalencies of 11 and 40%. The results indicate the degree of covalency of the Fe–S bonds plays a major role in determining the reaction pathway associated with oxygen exposure of iron thiolates. The X-ray structures of 1, 4, and 5 are reported.

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Acknowledgments

We wish to acknowledge Donald DuPré, Lucius Johnson, Jessica Koehler, and Jadwiga Kuta for assistance with the computational work. This work was supported by the National Science Foundation (CHE-0238137).

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  1. Department of Chemistry, University of Louisville, Louisville, KY, 40292, USA

    Martin G. O’Toole, Majda Kreso, Pawel M. Kozlowski, Mark S. Mashuta & Craig A. Grapperhaus

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  1. Martin G. O’Toole
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Correspondence to Craig A. Grapperhaus.

Electronic supplementary material

Electronic Supplementary Material: Calculated energies, experimental and calculated bond distances, and atomic contributions to Kohn–Sham molecular orbitals in PDF format, ESI-MS of 3 and LSS, IR spectrum for 3 (16O2 and 18O2), and crystallographic data for 1, 4, and 5 in CIF format. Crystallographic data for 1, 4, and 5 reported in this paper have been deposited with the Cambridge Crystallographic Data Centre (CCDC) as supplementary publication nos. CCDC-678256, CCDC-678257, and CCDC-678258. Copies of the data can be obtained free of charge from the CCDC (12 Union Road, Cambridge CB2 1EZ, UK; Tel: +44-1223-336408; Fax: +44-1223-336003; e-mail: deposit@ccdc.cam.ac.uk; Web site: http://www.ccdc.cam.ac.uk).

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O’Toole, M.G., Kreso, M., Kozlowski, P.M. et al. Spin-state-dependent oxygen sensitivity of iron dithiolates: sulfur oxygenation or disulfide formation. J Biol Inorg Chem 13, 1219–1230 (2008). https://doi.org/10.1007/s00775-008-0405-4

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