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Issue 35, 2014
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New insights into the chemistry of di- and trimetallic iron dithiolene derivatives. Structural, Mössbauer, magnetic, electrochemical and theoretical studies

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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)73-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.

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

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Article information


Submitted
19 May 2014
Accepted
30 Jun 2014
First published
01 Jul 2014

Dalton Trans., 2014,43, 13187-13195
Article type
Paper
Author version available

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

S. Bruña, I. Cuadrado, E. Delgado, C. J. Gómez-García, D. Hernández, E. Hernández, R. Llusar, A. Martín, N. Menéndez, V. Polo and F. Zamora, Dalton Trans., 2014, 43, 13187
DOI: 10.1039/C4DT01462F

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