Issue 2, 2016

Bimetallic iron–iron and iron–zinc complexes of the redox-active ONO pincer ligand

Abstract

A new bimetallic platform comprising a six-coordinate Fe(ONO)2 unit bound to an (ONO)M (M = Fe, Zn) has been discovered ((ONOcat)H3 = bis(3,5-di-tert-butyl-2-phenol)amine). Reaction of Fe(ONO)2 with either (ONOcat)Fe(py)3 or with (ONOq)FeCl2 under reducing conditions led to the formation of the bimetallic complex Fe2(ONO)3, which includes unique five- and six-coordinate iron centers. Similarly, the reaction of Fe(ONO)2 with the new synthon (ONOsq˙)Zn(py)2 led to the formation of the heterobimetallic complex FeZn(ONO)3, with a six-coordinate iron center and a five-coordinate zinc center. Both bimetallic complexes were characterized by single-crystal X-ray diffraction studies, solid-state magnetic measurements, and multiple spectroscopic techniques. The magnetic data for FeZn(ONO)3 are consistent with a ground state S = 3/2 spin system, generated from a high-spin iron(II) center that is antiferromagnetically coupled to a single (ONOsq˙)2− radical ligand. In the case of Fe2(ONO)3, the magnetic data revealed a ground state S = 7/2 spin system arising from the interactions of one high-spin iron(II) center, one high-spin iron(III) center, and two (ONOsq˙)2− radical ligands.

Graphical abstract: Bimetallic iron–iron and iron–zinc complexes of the redox-active ONO pincer ligand

Supplementary files

Article information

Article type
Edge Article
Submitted
13 Aug 2015
Accepted
27 Nov 2015
First published
08 Dec 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2016,7, 1594-1599

Bimetallic iron–iron and iron–zinc complexes of the redox-active ONO pincer ligand

J. L. Wong, R. F. Higgins, I. Bhowmick, D. X. Cao, G. Szigethy, J. W. Ziller, M. P. Shores and A. F. Heyduk, Chem. Sci., 2016, 7, 1594 DOI: 10.1039/C5SC03006D

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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