Isolation and Spectroscopic Properties of A-β-[PV_3W_9O_<40>]^<6-> Anion Salts and Their Isomerization to the α-Isomers

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<i>β</i>-Isomers of A-type vanadium-trisubstituted nonatungstophosphate anion salts were synthesized by a condensation of NaVO<sub>3</sub> and A-Na<sub>9</sub>[PW<sub>9</sub>O<sub>34</sub>]·7H<sub>2</sub>O in an aqueous hydrochloric acid and 1,4-dioxane mixed solution. Their geometries were characterized by IR, <sup>31</sup>P, <sup>51</sup>V, and <sup>183</sup>W NMR spectroscopies. The tetrabutylammonium salt of the <i>β</i>-isomer, A-<i>β</i>-(NBu<sup><i>n</i></sup><sub>4</sub>)<sub>4</sub>H<sub>2</sub>[PV<sub>3</sub>W<sub>9</sub>O<sub>40</sub>], isomerizes to the corresponding <i>α</i>-isomer both in the solid state and in solution under mild conditions, which can be directly followed by FT-IR and <sup>31</sup>P NMR spectroscopies. The kinetics of the isomerization in the solid state had a first-order rate constant at 40 °C, <i>k</i><sub>1</sub> = 2.19 × 10<sup>−7</sup> (s<sup>−1</sup>), together with Δ<i>H</i><sup>‡</sup> = 93.3 (kJ mol<sup>−1</sup>) and Δ<i>S</i><sup>‡</sup> = −77.3 (J K<sup>−1</sup> mol<sup>−1</sup>). On the other hand, A-<i>β</i>-Cs<sub>6</sub>[PV<sub>3</sub>W<sub>9</sub>O<sub>40</sub>] and A-<i>β</i>-(NBu<sup><i>n</i></sup><sub>4</sub>)<sub>6</sub>[PV<sub>3</sub>W<sub>9</sub>O<sub>40</sub>], which have no protons in the cation part, do not isomerize under the same conditions. The <i>β</i>-to-<i>α</i> isomerization is promoted by protonation at the bridging oxygen atom in the W–O–W bond of the polyanion.

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  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 69(2), 359-365, 1996-02-15

    The Chemical Society of Japan

参考文献:  22件中 1-22件 を表示

  • <no title>

    MISONO M.

    Proc. Int. Conf. Chem, Uses Molybdenum, 4th 1982, 289

    被引用文献1件

  • <no title>

    NOMIYA K.

    Bull. Chem. Soc. Jpn. 53, 3719, 1980

    被引用文献4件

  • <no title>

    FINKE R. G.

    Inorg. Chem. 28, 1573, 1989

    被引用文献2件

  • <no title>

    BURDETT J. K.

    J. Am. Chem. Soc. 112, 5366, 1990

    被引用文献3件

  • <no title>

    POPE M. T.

    Inorg. Chem. 14, 953, 1975

    被引用文献3件

  • <no title>

    BAKER L. C. W.

    J. Am. Chem. Soc. 92, 3794, 1970

    被引用文献3件

  • <no title>

    DOMAILLE P. J.

    Inorg. Chem. 25, 1239, 1986

    被引用文献4件

  • <no title>

    FINKE R. G.

    J. Am. Chem. Soc. 106, 7274, 1984

    被引用文献5件

  • <no title>

    FINKE R. G.

    J. Am. Chem. Soc. 108, 2947, 1986

    被引用文献4件

  • <no title>

    WEAKLEY T. J. R.

    J. Chem. Soc., Chem. Commun. 1984, 1406

    被引用文献3件

  • <no title>

    DOMAILLE P. J.

    J. Am. Chem. Soc. 108, 2108, 1986

    被引用文献3件

  • <no title>

    KAWAFUNE I.

    Chem. Lett. 1992, 1869

    被引用文献4件

  • <no title>

    ROBERT F.

    Acta Crystallogr., Sect. C. 37B, 318, 1981

    被引用文献1件

  • <no title>

    MOSSOBA M. M.

    Inorg. Chem. 27, 96, 1990

    被引用文献1件

  • <no title>

    ROBERT F.

    Bull Chem. Soc. Jpn. 67, 694, 1994

    被引用文献1件

  • <no title>

    DOMAILLE P. J.

    Inorg. Chem. 26, 2112, 1987

    被引用文献1件

  • <no title>

    KAWAFUNE I.

    Spectrochim. Acta, Pan A. 32, 587, 1976

    被引用文献1件

  • <no title>

    LEPARULO-LOFTUS M. A.

    Inorg. Chem. 22, 207, 1983

    被引用文献1件

  • <no title>

    DOMAILLE P. J.

    J. Am. Chem. Soc. 106, 7677, 1984

    DOI 被引用文献3件

  • <no title>

    OZEKI T.

    Acta Crystallogr. C47, 693, 1991

    DOI 被引用文献5件

  • <no title>

    MOSSOBA M. M.

    J. Am. Chem. Soc. 102, 6866, 1980

    DOI 被引用文献1件

  • <no title>

    ROCCHICCIOLI-DELTCHEFF C.

    Inorg. Chem. 23, 598, 1984

    DOI 被引用文献1件

各種コード

  • NII論文ID(NAID)
    10008899415
  • NII書誌ID(NCID)
    AA00580132
  • 本文言語コード
    ENG
  • 資料種別
    ART
  • ISSN
    00092673
  • データ提供元
    CJP書誌  J-STAGE 
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