Synthesis and some properties of anionic chloranilate complexes of iron(iii). Crystal and molecular structure of rubidium and cesium chloranilatoferrates |
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| Authors: | Z K Nikitina G V Shilov N S Ovanesyan V D Makhaev |
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| Institution: | 1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 prosp. Akad. Semenova, 142432, Chernogolovka, Moscow Region, Russian Federation
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| Abstract: | New anionic chloranilate complexes of iron(iii) CsFe(C6O4Cl2)2(H2O)2]·4H2O (1), RbFe(C6O4Cl2)2(H2O)2]·4H2O (2), Rb2Fe(C6O4Cl2)2(H2O)2]2·5H2O (3), Cs3Fe(C6O4Cl2)3 (4), (Bu4N)Fe(C6O4Cl2)2 (5), (Bu4N)4Fe2(C6O4Cl2)5 (6), and (R4N)3Fe(C6O4Cl2)3 (R = Pr (7), Bu (8), C5H11 (9)) were synthesized in an aqueous medium. The Mössbauer spectra of the synthesized chloranilatoferrates are characteristic of the high-spin state of FeIII in an octahedral oxygen coordination. The crystal and molecular structures of compounds 1–3 were determined by X-ray diffraction. The complex anions Fe(C6O4Cl2)2(H2O)2]2? involved in these compounds are composed of two chelate chloranilate ions and two water molecules trans-(1,2) or cis-coordinated (3) to the iron atom. Since tetraalkylammonium tris(chloranilato)ferrates 7–9 and binuclear complex 6 are soluble in many organic solvents, they are promising precursors for the synthesis of metal-organic coordination polymers. Tetrabutylammonium bis(chloranilato)ferrate (Bu4N)Fe(C6O4Cl2)2 (5) is the first example of the preparation of an anionic chloranilate complex of iron(iii) with a plausible chain structure in an aqueous medium. |
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