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Formation and Transformations of Polynuclear Hydroxo- and Oxotrimethylacetate Complexes of Ni(II) and Co(II)

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Abstract

Transformations of polymeric trimethylacetate complexes [M(OH) n (OOCCMe3)2 – n ] m (M = Ni (I) and Co (II)) and clusters Ni9(μ4-OH)3(μ3-OH)3(μ-O,O-OOCCMe3)(μ-O,O"-OOCCMe3)7(μ3-O,O,O"-OOCCMe3)3(μ4-O,O,O",O"-OOCCMe3)(HOOCCMe3)4(III) and Co6(μ3-OH)2(μ-OOCCMe3)10(HOOCCMe3)4(VIII), which are formed from Iand IIupon their recrystallization from nonpolar solvents, were studied. It was shown that the action of N-phenyl-o-phenylenediamine (L) on Ior IIIresults, depending on the solvent, in different tetranuclear clusters with the hydroxo bridges. For example, in benzene, the L2Ni4(μ3-OH)2(HOOCCMe3)4(μ-OOCCMe3)6complex (IX) is formed; its L molecules are coordinated in a monodentate way, whereas in acetonitrile, they chelate to give the {[o-C6H4(NH2)(NHPh)]2Ni4(μ3-OH)2(MeCN)2(OOCCMe3)2(μ-OOCCMe3)4} compound (X). Heating of Xin the presence of atmospheric oxygen yields IX, the mononuclear bissemiquinonediimine [o-C6H4(NH)(NPh)]2Ni complex (XI), and water. It was noted that the use of aniline in these reactions affords, independent of the nature of the solvent, only one (NH2C6H5)2Ni4(μ3-OH)2(HOOCCMe3)4(μ-OOCCMe3)6cluster (VI); in acetonitrile, this cluster is formed as the solvate VI· 2HOOCCMe3(VIa). When treated with ethanol, Iand IIIgive the Ni4(EtOH)6(μ3-OH)2(μ2-OOCCMe3)4(OOCCMe3)2cluster (V), which is structurally close to the known cobalt-containing analog IV. Thermolysis of IVin decalin at 170°С causes its dimerization, giving the octanuclear Co8(μ4-O)2(μ n -OOCCMe3)12complex (VII) with the tetradentate oxo bridges.

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Authors and Affiliations

  1. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 117907, Russia

    A. A. Sidorov, I. G. Fomina, S. S. Talismanov, G. G. Aleksandrov, V. M. Novotortsev, S. E. Nefedov & I. L. Eremenko

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  1. A. A. Sidorov
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  2. I. G. Fomina
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  3. S. S. Talismanov
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  4. G. G. Aleksandrov
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  5. V. M. Novotortsev
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  6. S. E. Nefedov
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  7. I. L. Eremenko
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Sidorov, A.A., Fomina, I.G., Talismanov, S.S. et al. Formation and Transformations of Polynuclear Hydroxo- and Oxotrimethylacetate Complexes of Ni(II) and Co(II). Russian Journal of Coordination Chemistry 27, 548–559 (2001). https://doi.org/10.1023/A:1011349727749

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