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Transformations of high spin MnII and FeII polymeric pivalates in reactions with pivalic acid and o-phenylenediamines
Authors:M A Kiskin  G G Aleksandrov  Zh V Dobrokhotova  V M Novotortsev  Yu G Shvedenkov  I L Eremenko
Institution:(1) N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prosp., 119991 Moscow, Russian Federation;(2) A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, 3 prosp. Akad. Lavrent’eva, 630090 Novosibirsk, Russian Federation
Abstract:The thermolysis and reactions of the polymeric high spin MnII and FeII complexes Mn(μ-OOCBut)2(HOEt)]n (1) and Fe(μ-OOCBut)2]n (3) with pivalic acid and o-phenylenediamines 1,2-(NH2)2C6H2R2 (R = H or Me) were studied. The synthesis of compound 1 performed with a deficiency of pivalate anions affords the antiferromagnetic chloropivalate polymer { (MeCN)(HOOCBut)(H2O)Mn5Cl(OH)(OOCBut)8·MeCN}n. The reaction of 1 with an excess of pivalic acid produces the antiferromagnetic polymer Mn4(OOCBut)8(HOOCBut)2]n. The analogous reaction of pivalic acid with polymer 3 gives the mononuclear complex Fe(η 1-OOCBut)21-HOOCBut)4 containing the high spin iron(II) atom as the major product. Study of the reactions of 3 with a deficiency (<1: 1) and an excess (>1: 1) of diamines demonstrated that the polymer {(η2-(NH2)2C6H4)2Fe(μ-OOCBut)2]Fe2(μ-OOCBut)4] · · 2MeCN}n is generated as the major product in the former case, whereas the mononuclear complexes Fe(η1-OOCBut)2η1-(NH2)2C6H4]4 and Fe(η1-OOCBut)2η2-(NH2)2C6H2Me21-(NH2)2C6H2Me2]2 are predominantly obtained in the latter case. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 779–792, May, 2006.
Keywords:iron(II) complexes  polynuclear manganese(II) complexes  carboxylate ligands  synthesis  X-ray diffraction study  magnetic properties  thermal decomposition
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