title: New insights into the chemistry of di- and trimetallic iron dithiolene derivatives. Structural, Mössbauer, magnetic, electrochemical and theoretical studies.
abstract: Reaction of Fe3(CO)12 with 1,2-dithiolene HSC6H2Cl2SH affords a mixture of complexes [Fe2(CO)6(μ-SC6H2Cl2S)] 1, [Fe2(SC6H2Cl2S)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 Fe(III) state (S(Fe) = 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.
authors.affiliation: Departamento de Química Inorgánica, Universidad Autónoma de Madrid, 28049 Madrid, Spain. esther.delgado@uam.es.
authors.forename: Sonia
authors.initials: S
authors.lastname: Bruña
authors.forename: Isabel
authors.initials: I
authors.lastname: Cuadrado
authors.forename: Esther
authors.initials: E
authors.lastname: Delgado
authors.forename: Carlos J
authors.initials: CJ
authors.lastname: Gómez-García
authors.forename: Diego
authors.initials: D
authors.lastname: Hernández
authors.forename: Elisa
authors.initials: E
authors.lastname: Hernández
authors.forename: Rosa
authors.initials: R
authors.lastname: Llusar
authors.forename: Avelino
authors.initials: A
authors.lastname: Martín
authors.forename: Nieves
authors.initials: N
authors.lastname: Menéndez
authors.forename: Victor
authors.initials: V
authors.lastname: Polo
authors.forename: Félix
authors.initials: F
authors.lastname: Zamora
mesh_terms: D055664:Electrochemical Techniques / Q000379:methods*; D005290:Ferric Compounds / Q000737:chemistry*; D005296:Ferrous Compounds / Q000737:chemistry*; D007501:Iron / Q000737:chemistry; D060306:Magnetometry / Q000379:methods*; D008962:Models, Theoretical; D015394:Molecular Structure; D015204:Spectroscopy, Mossbauer / Q000379:methods; D014961:X-Ray Diffraction
chemical_list: D005290:Ferric Compounds; D005296:Ferrous Compounds; D007501:Iron