Jump to main content
Jump to site search

Issue 22, 2015
Previous Article Next Article

Ambivalent binding between a radical-based pincer ligand and iron

Author affiliations

Abstract

A complex exhibiting valence delocalization was prepared from 3,5-bis(2-pyridyl)-1,2,4,6-thiatriazinyl (Py2TTA˙), an inherently redox active pincer-type ligand, coordinated to iron (Fe(Py2TTA)Cl2 (1)). Complex 1 can be prepared via two routes, either from the reaction of the neutral radical with FeCl2 or by treatment of the anionic ligand (Py2TTA) with FeCl3, demonstrating its unique redox behaviour. Electrochemical studies, solution absorption and solid-state diffuse reflectance measurements along with X-ray crystallography were carried out to elucidate the molecular and solid-state properties. Temperature- and field-dependent Mössbauer spectroscopy coupled with magnetic measurements revealed that 1 exhibits an isolated S = 5/2 ground spin state for which the low-temperature magnetic behaviour is dominated by exchange interactions between neighbouring molecules. This ground state is rationalized on the basis of DFT calculations that predict the presence of strong electronic interactions between the redox active ligand and metal. This interaction leads to the delocalization of β electron density over the two redox active centres and highlights the difficulty in assigning formal charges to 1.

Graphical abstract: Ambivalent binding between a radical-based pincer ligand and iron

Back to tab navigation

Supplementary files

Publication details

The article was received on 10 Apr 2015, accepted on 05 May 2015 and first published on 07 May 2015


Article type: Paper
DOI: 10.1039/C5DT01374G
Citation: Dalton Trans., 2015,44, 10516-10523
  • Open access: Creative Commons BY-NC license
  •   Request permissions

    Ambivalent binding between a radical-based pincer ligand and iron

    K. L. M. Harriman, A. A. Leitch, S. A. Stoian, F. Habib, J. L. Kneebone, S. I. Gorelsky, I. Korobkov, S. Desgreniers, M. L. Neidig, S. Hill, M. Murugesu and J. L. Brusso, Dalton Trans., 2015, 44, 10516
    DOI: 10.1039/C5DT01374G

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements