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Modular Bimetallic Complexes with a Sulfonamido-based Ligand

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Journal Dalton Trans
Specialty Chemistry
Date 2018 Aug 18
PMID 30118133
Citations 1
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Abstract

A series of bimetallic complexes prepared with the ligands N,N,N',N'-tetramethylethane-1,2-diamine (TMEDA) and N,N',N''-[2,2',2''-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido) ([MST]3-) is described. Four diiron compounds of the formulation (TMEDA)FeII(X)-(μ-OH)-FeIIIMST were prepared, in which the X- ligands are the anions OTf-, Br-, SCN-, or N3-. Additionally, two heterobimetallic compounds of the formulation (TMEDA)MII(OTf)-(μ-OH)-FeIIIMST (MII = CoII or NiII) were synthesized. All these compounds have similar spectroscopic and structural properties. The diiron compounds exhibit perpendicular-mode electron paramagnetic resonance spectra consistent with S = 1/2 spin ground states, which is expected for high-spin FeII and FeIII centres that are antiferromagnetically coupled. The heterobimetallic (TMEDA)NiII(OTf)-(μ-OH)-FeIIIMST complex had a spin state of S = 3/2 that also resulted from antiferromagnetic coupling between the high-spin NiII and FeIII centres. The modularity of this system is further demonstrated by the substitution of the TMEDA ligand with ethylenediamine (en); for this species two equivalents of en coordinate to the FeII centre to form [(en)2FeII-(μ-OH)-FeIIIMST]OTf. These results demonstrate that a modular bimetallic system has been developed in which the key components can be modified.

Citing Articles

Stepwise assembly of heterobimetallic complexes: synthesis, structure, and physical properties.

Lee J, Oswald V, Biswas S, Hill E, Ziller J, Hendrich M Dalton Trans. 2021; 50(23):8111-8119.

PMID: 34019606 PMC: 8418555. DOI: 10.1039/d1dt01021b.

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