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Issue 12, 2012
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Super reduced Fe4S4 cluster of Balch's dithiolene series

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A super reduced Fe4S4 cluster with a sulfur based radical, [NBu4]4[Fe3IIIFeII3-S)4(mnt)36−(mnt)1−˙]4−˙, (1) (mnt, maleonitrile dithiolate) which evolves H2S gas on treatment with acid under ambient conditions has been synthesized and structurally characterized. The Fe–S distances in 1 are in the range 2.246–2.383 Å, in stark contrast to that of the known n = −2 member of the series based on the [Fe43-S)4(S2C2R2)4]n unit (R = CF3, Ph) with Fe–S bond lengths of 2.149–2.186 Å. The EPR of 1 displays very weak signals at g, 4.03 and 2.38 along with a strong S-based radical EPR signal at g, 2.003 associated with five structured components tentatively assigned to hyperfine interaction arising out of the naturally abundant 57Fe with <A> = 88 G. The EPR profile resembles the reduced Fe–S cluster of CO inhibited Clostridium pasteurianum W5 hydrogenase or the Fe4S4 centers of wild-type enzyme, IspH treated with HMBPP or IPP.

Graphical abstract: Super reduced Fe4S4 cluster of Balch's dithiolene series

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The article was received on 15 Nov 2011, accepted on 19 Dec 2011 and first published on 08 Feb 2012

Article type: Paper
DOI: 10.1039/C2DT12184K
Citation: Dalton Trans., 2012,41, 3536-3540
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    Super reduced Fe4S4 cluster of Balch's dithiolene series

    A. Begum, G. Moula, M. Bose and S. Sarkar, Dalton Trans., 2012, 41, 3536
    DOI: 10.1039/C2DT12184K

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