Treatment of [Fe2(mu-pdt)(CO)6] [pdt=S(CH2)3S] with dppe (Ph2PCH2CH2PPh2) in refluxing toluene affords the asymmetric complex [Fe2(mu-pdt)(CO)4(dppe)] (1). Protonation of 1 with HBF4-Et2O in CH2Cl2 gives at room temperature the mu-hydrido derivative [Fe2(mu-pdt)(CO)4(dppe)(mu-H)](BF4) (2). Monitoring the reaction by 1H, 31P, and 13C NMR at low temperature reveals unambiguously that the process of the protonation of 1 implies terminal hydride intermediates.

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International audienceThe 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

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Novel asymmetrically substituted azadithiolate compounds [Fe2(CO)4(kappa2-dppe){micro-SCH2N(R)CH2S}] (R=iPr, 1a; CH2CH2OCH3, 1b; CH2C6H5, 1c) have been synthesized by treatment of [Fe2(CO)6(micro-adt)] [adt=SCH2N(R)CH2S, with R=iPr, CH2CH2OCH3, CH2C6H5] with dppe (dppe=Ph2PCH2CH2PPh2) in refluxing toluene in the presence of Me3NO. 1a-c have been characterized by single-crystal X-ray diffraction analyses. The electrochemical investigation of 1a-c and of [Fe2(CO)4(kappa2-dppe)(micro-pdt)] (1d) [pdt=S(CH2)3S] in MeCN- and THF-[NBu4][PF6] has demonstrated that the electrochemical reduction of 1a-d gives rise to an Electron-transfer-catalyzed (ETC) isomerization to the symmetrical isomers 2a-d where the dppe ligand bridges the iron centers. Compounds 2a-d were characterized by IR and NMR spectroscopy, elemental analysis, and X-ray crystallography for 2a.