Jump to main content
Jump to site search

Issue 20, 2017
Previous Article Next Article

Synthetic, structural and magnetic implications of introducing 2,2′-dipyridylamide to sodium-ferrate complexes

Author affiliations

Abstract

Using a transamination approach to access novel Fe(II) complexes, this study presents the synthesis, X-ray crystallographic and magnetic characterisation of a series of new iron complexes containing the multifunctional 2,2-dipyridylamide (DPA) ligand using iron bis(amide) [{Fe(HMDS)2}2] and sodium ferrate [{NaFe(HMDS)3}] (1) as precursors (HMDS = 1,1,1,3,3,3-hexamethyldisilazide). Reactions of DPA(H) with 1 show exceptionally good stoichiometric control, allowing access to heteroleptic [(THF)2·NaFe(DPA)(HMDS)2] (3) and homoleptic [{THF·NaFe(DPA)3}] (4) by using 1 and 3 equivalents of DPA(H), respectively. Linking this methodology and co-complexation, which is a more widely used approach to prepare heterobimetallic complexes, 3 can also be prepared by combining NaHMDS with heteroleptic [{Fe(DPA)(HMDS)}2] (2). In turn, 2 has been also synthesised and structurally defined by reacting [{Fe(HMDS)2}2] with two equivalents of DPA(H). Structural studies demonstrate the coordination flexibility of the N-bridged bis(heterocycle) ligand DPA, with 2 and 3 exhibiting discrete monomeric motifs, whereas 4 displays a much more intricate supramolecular structure, with one of its DPA ligands coordinating in an anti/anti fashion (as opposed to 2 and 3 where DPA shows a syn/syn conformation), which facilitates propagation of the structure via its central amido N. Magnetic studies confirmed the high-spin electron configuration of the iron(II) centres in all three compounds and revealed the existence of weak ferromagnetic interactions in dinuclear compound 2 (J = 1.01 cm−1).

Graphical abstract: Synthetic, structural and magnetic implications of introducing 2,2′-dipyridylamide to sodium-ferrate complexes

Back to tab navigation

Supplementary files

Publication details

The article was received on 12 Apr 2017, accepted on 26 Apr 2017 and first published on 26 Apr 2017


Article type: Paper
DOI: 10.1039/C7DT01319A
Citation: Dalton Trans., 2017,46, 6683-6691
  •   Request permissions

    Synthetic, structural and magnetic implications of introducing 2,2′-dipyridylamide to sodium-ferrate complexes

    L. C. H. Maddock, I. Borilovic, J. McIntyre, A. R. Kennedy, G. Aromí and E. Hevia, Dalton Trans., 2017, 46, 6683
    DOI: 10.1039/C7DT01319A

Search articles by author

Spotlight

Advertisements