The Characterization of Oligomeric Iron(II)-tetraoxime Complexes

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概要

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• Several polymeric iron(II) chelates with tetraoxime ligands,<BR>CH<SUB>3</SUB>C(NOH)C(NOH)–\overset(α)CH<SUB>2</SUB>–\overset(β)CH<SUB>2</SUB>–(CH<SUB>2</SUB>)<I><SUB>n</SUB></I>–\overset(β)CH<SUB>2</SUB>–\overset(α)CH<SUB>2</SUB>–C(NOH)C(NOH)CH<SUB>3</SUB>,<BR>where <I>n</I>=2 and 6, were characterized. They show a ligand-to-iron molar ratio of 1 : 1, corresponding to a planar arrangement of the ferrous ion and the four oxime nitrogens; two pyridine or methylpyridine substituents are axially coordinated to the central metal ion. The complexes are diamagnetic in the solid state, and their absorption spectra closely resemble those of the monomeric ferrous dimethylglyoxime compounds. The molecular weight, determined in a pyridine solution by vapor-pressure osmometry (2800 for –(CH<SUB>2</SUB>)<SUB>2</SUB>– and 3100 for –(CH<SUB>2</SUB>)<SUB>6</SUB>–), corresponds to 5 or 6 Fe–N<SUB>4</SUB> units within the polymer chain. An NMR investigation including tetraoxime ligands with both aliphatic and aromatic linkages, as well as the corresponding chelates, shows that the protons in the α or in the β position to the oxime groups do not undergo any shift upon chelation. The electronic spectral data and NMR data provide no evidence that the Fe(II) chelate rings within the polymer chain are affected by one another.

• 公益社団法人 日本化学会の論文

著者

• Shinra Koichiro

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Masuda Isao

  Department of Chemistry, Faculty of Science, Fukuoka University

• Backes Joseph

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

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