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Title

New insights into the chemistry of di- and trimetallic iron dithiolene derivatives. Structural, Mössbauer, magnetic, electrochemical and theoretical studies

AuthorsBruña, S.; Cuadrado, I.; Delgado, E.; Gómez-García, C.J.; Hernández, D.; Hernández, E.; Llusar, R.; Martín, A.; Menéndez, N.; Polo, Víctor; Zamora, F.
Issue Date2014
PublisherRoyal Society of Chemistry
CitationDalton Transactions 43: 13187- 13195 (2014)
AbstractReaction of Fe3(CO)12 with 1,2-dithiolene HSC 6H2Cl2SH affords a mixture of complexes [Fe2(CO)6(μ-SC6H2Cl 2S)] 1, [Fe2(SC6H2Cl 2S)4] 2 and [Fe3(CO) 7(μ3-SC6H2Cl2S) 2] 3. In the course of the reaction the trimetallic cluster 3 is first formed and then converted into the known dinuclear compound 1 to afford finally the neutral diiron tetrakis(dithiolato) derivative 2. Compounds 2 and 3 have been studied by Mössbauer spectroscopy, X-ray crystallography and theoretical calculations. In compound 2 the metal atoms are in an intermediate-spin FeIII state (SFe = 3/2) and each metal is bonded to a bridging dithiolene ligand and a non-bridging thienyl radical (S = 1/2). Magnetic measurements show a strong antiferromagnetic coupling in complex 2. Cyclic voltammetry experiments show that the mixed valence trinuclear cluster 3 undergoes a fully reversible one electron reduction. Additionally, compound 3 behaves as an electrocatalyst in the reduction process of protons to hydrogen. © 2014 The Royal Society of Chemistry.
URIhttp://hdl.handle.net/10261/167791
Identifiersdoi: 10.1039/c4dt01462f
issn: 1477-9234
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