Issue 11, 2023, Issue in Progress

NiII and CuII complexes of a salen ligand bearing ferrocenes in its secondary coordination sphere

Abstract

Herein, we report the synthesis, spectroscopic characterization and electrochemical investigation of the NiII and CuII complexes of a novel Sal ligand bearing two ferrocene moieties attached at its diimine linker, M(Sal)Fc. The electronic spectra of M(Sal)Fc are near identical to its phenyl-substituted counterpart, M(Sal)Ph, indicating the ferrocene moieties exist in the secondary coordination sphere of M(Sal)Fc. The cyclic voltammograms of M(Sal)Fc exhibit an additional two-electron wave in comparison to M(Sal)Ph, which is assigned to the sequential oxidation of the two ferrocene moieties. The chemical oxidation of M(Sal)Fc, monitored by low temperature UV-vis spectroscopy, supports the formation of a mixed valent FeIIFeIII species followed by a bis(ferrocenium) species upon sequential addition of one and two equivalents of chemical oxidant. The addition of a third equivalent of oxidant to Ni(Sal)Fc yielded intense near-IR transitions that are indicative of the formation of a fully delocalized Sal-ligand radical (SalĖ™), while the same addition to Cu(Sal)Fc yielded a species that is currently under further spectroscopic investigation. These results suggest the oxidation of the ferrocene moieties of M(Sal)Fc does not affect the electronic structure of the M(Sal) core, and these are thus in the secondary coordination sphere of the overall complex.

Graphical abstract: NiII and CuII complexes of a salen ligand bearing ferrocenes in its secondary coordination sphere

Supplementary files

Article information

Article type
Paper
Submitted
02 Dec 2022
Accepted
24 Feb 2023
First published
06 Mar 2023
This article is Open Access
Creative Commons BY license

RSC Adv., 2023,13, 7293-7299

NiII and CuII complexes of a salen ligand bearing ferrocenes in its secondary coordination sphere

R. Sailer, W. VandeVen, K. Teindl and L. Chiang, RSC Adv., 2023, 13, 7293 DOI: 10.1039/D2RA07671C

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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