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DOI: 10.1039/A707008J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 713-718

Tetranuclear iron(III) complexes with amino acids involving a planar (µ-oxo)(µ-hydroxo)bis(µ-alkoxo)bis(µ-carboxylato)tetrairon core[hair space]†

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Tomoaki Tanase, Tomoko Inagaki, Yasuko Yamada, Masako Kato, Emi Ota, Mikio Yamazaki, Mitsunobu Sato, Wasuke Mori, Kazuya Yamaguchi, Masahiro Mikuriya, Masashi Takahashi, Masuo Takeda, Isamu Kinoshita and Shigenobu Yano

Abstract

Reactions of FeIII(NO3)3·9H2O with 0.5 equivalent of 2-hydroxypropane-1,3-diamine-N,N,N′,N′-tetraacetic acid (H5dhpta) and an excess of amino acid [glycine (Gly) or L-alanine (L-Ala)] in water with the pH adjusted to ca. 5 by a solution of NaOH gave pale green crystals formulated as Na[Fe4(dhpta)2(µ-O)(µ-OH)(O2CCHRNH3)2] (R = H 1 or CH3 2) in moderate yields. The tetrairon(III) complexes were characterized by elemental analyses, IR and 57Fe Mössbauer spectra, variable-temperature magnetic susceptibility, and X-ray crystallographic and absorption analyses. The structure of 2·6H2O was determined by X-ray crystallography to comprise a (µ-oxo)(µ-hydroxo)bis(µ-alkoxo)bis(µ-carboxylato)tetrairon(III) cluster core bridged by two dhpta and two amino acid ligands. Two identical dinuclear iron(III) units [Fe(1)Fe(2) and Fe(3)Fe(4)] are each co-ordinated by a pentadentate dhpta ligand. The Fe(1) and Fe(4) are then bridged by the carboxylate of an amino acid and an oxo group, with the Fe(2) and Fe(3) similarly linked. The central two oxo groups are protonated to form a strongly hydrogen bonded (O–H–O)3– bridge [O[hair space][hair space]· · ·[hair space][hair space]O 2.426(4) Å]. The average Fe[hair space][hair space]· · ·[hair space][hair space]Fe distance for the µ-alkoxo dinuclear units is 3.692 Å (intradimer) and that for the bis(µ-carboxylato)(µ-oxo/hydroxo)diiron units is 3.463 Å (interdimer), both being in accord with the corresponding values from EXAFS analyses. The two L-alanine moieties are in zwitterionic form and act as interdimer bridging ligands with the carboxylate groups. The Na+ counter cation is well packed between the tetrairon(III) complex anions, resulting in an infinite chain aggregation. The 57Fe Mössbauer spectrum for 2·6H2O clearly demonstrated that the four iron sites are equivalent, being in a high-spin octahedral iron(III) state. The variable-temperature magnetic susceptibility measurement for 2·6H2O showed modest antiferromagnetism with an interdimer coupling constant (J) of –42.3 cm–1 and an intradimer coupling constant (J′) of –20.8 cm–1.

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