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Non-innocent bma ligand in a dissymetrically disubstituted diiron dithiolate related to the active site of the [FeFe] hydrogenases

Abstract : The purpose of the present study was to evaluate the use of a non-innocent ligand as a surrogate of the anchored [4Fe4S] cubane in a synthetic mimic of the [FeFe] hydrogenase active site. Reaction of 2,3-bis(diphenylphosphino) maleic anhydride (bma) with [Fe2(CO)6(µ-pdt)] (propanedithiolate, pdt = S(CH2)3 S) in the presence of Me3NO-2H2O afforded the monosubstituted derivative [Fe2(CO)5(Me2NCH2PPh2)(µ-pdt)] (1). This results from the decomposition of the bma ligand and the apparent C–H bond cleavage in the released trimethylamine. Reaction under photolytic conditions afforded [Fe2(CO)4(bma)(µ-pdt)] (2). Compounds 1 and 2 were characterized by IR, NMR and X-ray diffraction. Voltammetric study indicated that the primary reduction of 2 is centered on the bma ligand.
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https://hal.univ-brest.fr/hal-01577400
Contributor : Nicolas Renard <>
Submitted on : Friday, August 25, 2017 - 3:23:49 PM
Last modification on : Thursday, October 3, 2019 - 8:50:07 AM

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Youtao Si, Kévin Charreteur, Jean-François Capon, Frederic Gloaguen, François Y. Pétillon, et al.. Non-innocent bma ligand in a dissymetrically disubstituted diiron dithiolate related to the active site of the [FeFe] hydrogenases. Journal of Inorganic Biochemistry, Elsevier, 2010, 104 (10), pp.1038 - 1042. ⟨10.1016/j.jinorgbio.2010.05.011⟩. ⟨hal-01577400⟩

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