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

Dalton transactions (Cambridge, England : 2003)

PubMedID: 25027173

Bruña S, Cuadrado I, Delgado E, Gómez-García CJ, Hernández D, Hernández E, Llusar R, Martín A, Menéndez N, Polo V, Zamora F. New insights into the chemistry of di- and trimetallic iron dithiolene derivatives. Structural, Mössbauer, magnetic, electrochemical and theoretical studies. Dalton Trans. 2014;.
Reaction of Fe3(CO)12 with 1,2-dithiolene HSC6H2Cl2SH affords a mixture of complexes [Fe2(CO)6(µ-SC6H2Cl2S)] , [Fe2(SC6H2Cl2S)4] and [Fe3(CO)7(µ3-SC6H2Cl2S)2] . In the course of the reaction the trimetallic cluster is first formed and then converted into the known dinuclear compound to afford finally the neutral diiron tetrakis(dithiolato) derivative . Compounds and have been studied by Mössbauer spectroscopy, X-ray crystallography and theoretical calculations. In compound the metal atoms are in an intermediate-spin Fe(III) 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 . Cyclic voltammetry experiments show that the mixed valence trinuclear cluster undergoes a fully reversible one electron reduction. Additionally, compound behaves as an electrocatalyst in the reduction process of protons to hydrogen.