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Transformations of high spin MnII and FeII polymeric pivalates in reactions with pivalic acid and o-phenylenediamines

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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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Authors and Affiliations

  1. N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prosp., 119991, Moscow, Russian Federation

    M. A. Kiskin, G. G. Aleksandrov, Zh. V. Dobrokhotova, V. M. Novotortsev & I. L. Eremenko

  2. A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, 3 prosp. Akad. Lavrent’eva, 630090, Novosibirsk, Russian Federation

    Yu. G. Shvedenkov

Authors
  1. M. A. Kiskin
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  2. G. G. Aleksandrov
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  3. Zh. V. Dobrokhotova
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  4. V. M. Novotortsev
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  5. Yu. G. Shvedenkov
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  6. I. L. Eremenko
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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

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