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)2(η1-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)2[η1-(NH2)2C6H4]4 and Fe(η1-OOCBut)2[η2-(NH2)2C6H2Me2][η1-(NH2)2C6H2Me2]2 are predominantly obtained in the latter case.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 779–792, May, 2006.
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Kiskin, M.A., Aleksandrov, G.G., Dobrokhotova, Z.V. et al. Transformations of high spin MnII and FeII polymeric pivalates in reactions with pivalic acid and o-phenylenediamines. Russ Chem Bull 55, 806–820 (2006). https://doi.org/10.1007/s11172-006-0337-5
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DOI: https://doi.org/10.1007/s11172-006-0337-5