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Issue 15, 2017
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A trigonal prismatic anionic iron(III) complex of a radical o-iminobenzosemiquinonate derivative: structural and spectral analyses

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Abstract

A new iron(III) complex, [Et3NH][FeIII(L2−˙)2] (1) with a substituted o-aminophenol based ligand is reported. Complex 1 is an anionic complex with a triethylammonium cation in the lattice. It contains two O,O,N-coordinated o-iminobenzosemiquinonate(2−) radical anions with an Fe(III) centre in a high-spin configuration. The crystal structure of 1 was determined by X-ray diffraction, which revealed a trigonal prismatic coordination environment whose electronic structure was established by various physical methods including EPR, Mössbauer spectroscopy and variable-temperature (2–300 K) magnetic susceptibility measurements. Electrochemical analysis indicated primarily ligand-centred redox processes. Complex 1 retained the high-spin character of Fe(III) throughout the temperature range studied (2–300 K) and exhibited, as expected, strong antiferromagnetic coupling operating between two radicals (SR = 1/2) and the high-spin Fe(III) centre (SFe = 5/2), yielding a St = 3/2 as the ground state. This was confirmed by means of DFT calculations (M06-2X/6-31+G*) and a spin density analysis of the high spin and low spin configurations.

Graphical abstract: A trigonal prismatic anionic iron(iii) complex of a radical o-iminobenzosemiquinonate derivative: structural and spectral analyses

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Publication details

The article was received on 11 Apr 2017, accepted on 01 Jun 2017 and first published on 02 Jun 2017


Article type: Paper
DOI: 10.1039/C7NJ01212H
Citation: New J. Chem., 2017,41, 7283-7291
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    A trigonal prismatic anionic iron(III) complex of a radical o-iminobenzosemiquinonate derivative: structural and spectral analyses

    S. Saha, C. Roy Choudhury, C. J. Gómez-García, S. Benmansour, E. Garribba, A. Frontera, C. Rizzoli and S. Mitra, New J. Chem., 2017, 41, 7283
    DOI: 10.1039/C7NJ01212H

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