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Exo-iron centers linked to MoFeS clusters

Abstract : Monocubane clusters with exo-iron atoms were synthesized from the iron-bridged dicubane [NEt4]3[Mo2Fe7S 8(SEt)12] by reactions with π-acid ligands. The structures of two derivatives, [NEt4][MoFe3S4X3(μ-SEt) 3Fe(CNtBu)3], X = Cl or PhS, have been established by X-ray crystallography. Electrochemical and Mössbauer data showed that the cubane core retains the _MoFe3S4₃+ redox level of the parent material and that the exo-iron centre is in the low-spin iron(II) state. Infrared and electrochemical data showed that there is little electronic interaction between the cubane and exo-iron centres. The parent complex possesses a low-spin bridging iron(III) centre. This centre undergoes slow electron transfer which is ascribed to spin-state reorganisation to high-spin FeII. Reduction of the cubane units leads to reversible deco-ordination of a bridging thiolate group from a molybdenum centre.
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Submitted on : Thursday, April 19, 2018 - 2:49:41 PM
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F. Barrière, D.J. Evans, D.L. Hughes, S.K. Ibrahim, J. Talarmin, et al.. Exo-iron centers linked to MoFeS clusters. Journal of the Chemical Society - Dalton Transactions, 1999, pp.957--964. ⟨hal-01771398⟩

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