Issue 63, 2020, Issue in Progress
From the journal:

RSC Advances

Syntheses, spectroscopic, redox, and structural properties of homoleptic Iron(III/II) dithione complexes†

Kyle J. Colston,a   Sara A. Dille,a   Benjamin Mogesa,b   Jacilynn Brant,c   Victor N. Nemykin,d   Matthias Zellere  and  Partha Basu ORCID logo *a  

* Corresponding authors

a Department of Chemistry and Chemical Biology, Indiana University-Purdue University, Indianapolis, IN, USA
E-mail: basup@iupui.edu

b Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh PA, USA

c The Air Force Research Laboratory, Wright-Patterson AFB, OH, USA

d Department of Chemistry, University of Tennessee, Knoxville, TN, USA

e Department of Chemistry, Purdue University, West Layfette, IN, USA

Abstract

Two sets of FeIII/II dithione complexes [FeII(iPr2Dt0)3][PF6]2 ([1][PF6]2), [FeII(Me2Dt0)3][PF6]2 ([2][PF6]2), and [FeIII(iPr2Dt0)3][PF6]3 ([3][PF6]3), [FeIII(Me2Dt0)3][PF6]3 ([4][PF6]3), and compound [FeIII(iPr2Dt0)3][FeCl4][PF]2 ([3][FeCl4][PF6]2) were synthesized from N,N′-diisopropyl piperazine-2,3-dithione (iPr2Dt0) and N,N′-dimethyl piperazine-2,3-dithione (Me2Dt0) ligands. Complexes [1][PF6]2–[4][PF6]3 have been characterized by NMR, IR, and UV-visible spectroscopies, and by electrochemistry. The molecular structures of [2][PF6]2 and [3][FeCl4][PF6]2 have been determined by X-ray crystallography. Complexes [2][PF6]2 and [3][FeCl4][PF6]2 both crystallized in the monoclinic space group P21/n. Both complexes exhibit distorted octahedral geometry and the three coordinated ligands in each complex exhibit different dithione folding. Complexes [1][PF6]2–[4][PF6]3 exhibit a single FeIII/II based couple and three quasi-reversible ligand-based redox couples. The electronic spectra of [1][PF6]2–[4][PF6]3 show intense MLCT bands that indicate strong mixing between metal and ligand orbitals. DFT calculations were used to provide a framework for understanding the electronic origin of their redox chemistry and spectroscopic features.

Graphical abstract: Syntheses, spectroscopic, redox, and structural properties of homoleptic Iron(III/II) dithione complexes

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Article information

DOI
https://doi.org/10.1039/D0RA07371G
Article type
Paper
Submitted
27 Aug 2020
Accepted
10 Oct 2020
First published
16 Oct 2020
This article is Open Access
Creative Commons BY-NC license

RSC Adv., 2020,10, 38294-38303

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Syntheses, spectroscopic, redox, and structural properties of homoleptic Iron(III/II) dithione complexes

K. J. Colston, S. A. Dille, B. Mogesa, J. Brant, V. N. Nemykin, M. Zeller and P. Basu, RSC Adv., 2020, 10, 38294 DOI: 10.1039/D0RA07371G

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