- Synthesis, structure, and properties of a new trinuclear iron cluster, [(MeOH)(H2O)2Fe3(μ 3-O)(μ-OOCC6H4OCH2C 5H4NH)6](CIO4)7 · · 8MeOH · 3.5H2O
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Reactions of iron(III) salts with a new bidentate ligand, which is potentially capable of forming binuclear iron complexes upon complexation, were studied. Under various conditions, we succeeded in isolating only the trinuclear cationic complex [FeIII3(O2CR)6(μ 3-O)]7+ (1), where RCO2 is 2-(pyrid-2-ylmethoxy)benzoic acid protonated at the pyridyl moiety. The structure of 1 was established by spectral, magnetic, and X-ray structural studies. Cyclic voltammetry in MeCN in the temperature range from -35 to 20°C demonstrated that 1 undergoes successive FeIII→FeII reduction in three one-electron stages, which is indicative of the electronic interaction between iron atoms in the complex.
- Trukhan,Eremenko,Ovanesyan,Pasynskii,Petrunenko,Strelets,Shteinman
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- A stereodynamic tripodal ligand with three different coordinating arms: Synthesis and zinc(II), copper(I) complexation study
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A tetradentate tripodal ligand containing a chiral center and three different coordinating arms was designed and synthesized. Its complexation properties with ZnII and CuI were studied by NMR and optical spectroscopy. NMR experiments demonstrated the formation of two diastereomers, indicating the stabilization of the central tertiary amine configuration by metal coordination. The inversion of pyramidalization of the central tertiary amine of the ligand was found to be highly dependent upon metal ion, solvent, and temperature. Dynamic NMR measurements were used to estimate the energy of activation required for nitrogen atom inversion. Finally, absorption and circular dichroism measurements confirmed the expectation that metal complexes of the ligand gave rise to circular dichroism but that such spectra were not characterized by exciton-coupling, in contrast to previously described ligands containing two identical arms with strong chromophores.
- Liang, Jian,Canary, James W.
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experimental part
p. 24 - 33
(2011/10/08)
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