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

作者：Bruna Sonia; Cuadrado Isabel; Delgado Esther^*; Gomez Garcia Carlos J; Hernandez Diego; Hernandez Elisa; Llusar Rosa; Martin Avelino; Menendez Nieves; Polo Victor; Zamora Felix

来源：Dalton Transactions, 2014, 43(35): 13187-13195.

DOI：10.1039/c4dt01462f

Reaction of Fe-3(CO)(12) with 1,2-dithiolene HSC6H2Cl2SH affords a mixture of complexes [Fe-2(CO)(6)(mu-SC6H2Cl2S)] 1, [Fe-2(SC6H2Cl2S)(4)] 2 and [Fe-3(CO)(7)(mu(3)-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 Mossbauer 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 antiferro-magnetic 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.

• 出版日期2014-9-21