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Complexes of ZrIV and HfIV with monolacunary Keggin-and Dawson-type anions

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Abstract

The reactions of the tetranuclear hydroxo complexes [M4(µ2-OH)8(H2O)16]8+ (M = Zr or Hf) with the lacunary Keggin-type ([α-PW11O39]7−) and Dawson-type ([α 2-P2W17O61]10−) phosphotungstates in aqueous solutions produce the sandwich polyoxometalate complexes [M(α-PW11O39)2]10− (M = Zr (1) or Hf (2)) and [M(α 2-P2W17O61)2]16− (M = Zr (3) and Hf (4)). The complexes were isolated and structurally characterized as salts with potassium and dimethylammonium cations. The zirconium and hafnium atoms have a square antiprismatic coordination environment (coordination number is 8). In all complexes, the mutual arrangement of the ligands corresponds to the syn isomer. Hafnium complexes 2 and 4 are the first structurally characterized polyoxometalate complexes of this metal. The structures of the resulting compounds were confirmed also by 31P NMR spectroscopy in solution.

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Authors and Affiliations

  1. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 prosp. Akad. Lavrentieva, 630090, Novosibirsk, Russian Federation

    M. N. Sokolov, E. V. Chubarova, E. V. Peresypkina, A. V. Virovets & V. P. Fedin

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  1. M. N. Sokolov
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  2. E. V. Chubarova
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  3. E. V. Peresypkina
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  4. A. V. Virovets
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  5. V. P. Fedin
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Correspondence to M. N. Sokolov.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 214–218, February, 2007.

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Sokolov, M.N., Chubarova, E.V., Peresypkina, E.V. et al. Complexes of ZrIV and HfIV with monolacunary Keggin-and Dawson-type anions. Russ Chem Bull 56, 220–224 (2007). https://doi.org/10.1007/s11172-007-0036-x

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  • DOI: https://doi.org/10.1007/s11172-007-0036-x

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