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Issue 12, 2007
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Electrochemical and theoretical investigations of the reduction of [Fe2(CO)5L{μ-SCH2XCH2S}] complexes related to [FeFe] hydrogenase

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Abstract

The complexes [Fe2(CO)6{μ-SCH2N(R)CH2S}] (R = CH2CH2OCH3, 1a; R = iPr, 1b) and [Fe2(CO)6(μ-pdt)] 2 (pdt = S(CH2)3S) are structural analogues of the [2Fe]H subsite of [FeFe]H2ases. Electrochemical investigation of 1 and 2 in MeCN–[NBu4][PF6] under Ar and under CO has demonstrated that the reduction can be resolved into two one-electron transfer steps by using fast scan cyclic voltammetry. At slow scan rates the reduction of 1 tends towards a two-electron process owing to the fast disproportionation of the anion, while the two-electron reduction of 2 is clearly favoured in the presence of CO. Substitution of a CO ligand in 2 by a N-heterocyclic carbene results in the destabilisation of the anion. Thus, in MeCN–, thf- or CH2Cl2–[NBu4][PF6], the electrochemical reduction of Fe2(CO)5LNHC(μ-pdt)] 3 (LNHC = 1,3-bis(methyl)-imidazol-2-ylidene, 3a; 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, 3b) occurs in a single-step, two-electron process at moderate scan rates; under appropriate conditions this process can be separated into two one-electron steps. Density Functional Theory calculations successfully rationalize the effects of the S-to-S linkage on the electrochemistry of the complexes.

Graphical abstract: Electrochemical and theoretical investigations of the reduction of [Fe2(CO)5L{μ-SCH2XCH2S}] complexes related to [FeFe] hydrogenase

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Publication details

The article was received on 19 Jun 2007, accepted on 18 Jul 2007 and first published on 17 Aug 2007


Article type: Paper
DOI: 10.1039/B709273C
Citation: New J. Chem., 2007,31, 2052-2064
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    Electrochemical and theoretical investigations of the reduction of [Fe2(CO)5L{μ-SCH2XCH2S}] complexes related to [FeFe] hydrogenase

    J. Capon, S. Ezzaher, F. Gloaguen, F. Y. Pétillon, P. Schollhammer, J. Talarmin, T. J. Davin, J. E. McGrady and K. W. Muir, New J. Chem., 2007, 31, 2052
    DOI: 10.1039/B709273C

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