Variable-temperature and variable-pressure nitrogen-14 NMR studies on the exchange reaction of different nitriles at the nickel(II) ion.
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The activation parameters for the exchange reaction of several nitriles at the nickel(II) ion have been determined for the nickel(II) trifluoromethanesulfonate solutions by means of the <SUP>14</SUP>N NMR line broadening method at various temperatures and pressures up to 220 MPa. Values of activation enthalpy (Δ<I>H</I><SUP>\neweq</SUP>/kJ mol<SUP>−1</SUP>), activation entropy (Δ<I>S</I><SUP>\neweq</SUP>/J mol<SUP>−1</SUP> K<SUP>−1</SUP>), and activation volume at zero pressure (Δ<I>V</I><SUB>0</SUB><SUP>\neweq</SUP>/cm<SUP>3</SUP> mol<SUP>−1</SUP>) for the exchange of various nitriles are respectively as follows: 41.4±0.5, −30±2, and +12.0±0.4 in acetonitrile; 42.0±0.4, −25±2, and +13.7±0.5 in propionitrile; 43.3±0.7, −23±2, and +13.1±0.5 in butyronitrile; 43.3±0.5, −19±2, and +12.4±0.6 in isobutyronitrile; 47.1±1.2, −10±4, and +14.4±0.4 in valeronitrile; 51.6±1.9, +4±6, and +13.1±0.6 in benzonitrile. The activation volume varies little in spite of the large variation of the molar volume of nitriles. The activation energy (<I>E</I><SUB>Q</SUB>/kJ mol<SUP>−1</SUP>) and the activation volume at zero pressure (Δ<I>V</I><SUB>q</SUB><SUP>\neweq</SUP> cm<SUP>3</SUP> mol<SUP>−1</SUP>) for the reorientation of nitrile molecules around the axis perpendicular to the C≡N bond were also determined to be respectively as follows: 7.4±0.1 and +8.3±0.4 for acetonitrile; 8.1±0.1 and +9.5±0.2 for propionitrile; 9.2±0.1 and +9.7±0.3 for butyronitrile; 9.1±0.1 and +11.3±0.2 for isobutyronitrile; 10.7±0.2 and +11.9±0.2 for valeronitrile; 12.5±0.2, and +13.5±0.2 for benzonitrile. Both <I>E</I><SUB>Q</SUB> and Δ<I>V<SUB>q</SUB></I><SUP>\neweq</SUP> increase with increasing bulkiness of the substituent to the cyano group.
- 公益社団法人 日本化学会の論文
著者
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Funahashi Shigenobu
Laboratory Of Analytical Chemistry Department Of Chemistry Faculty Of Science Nagoya University
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Tanaka Motoharu
Laboratory of Analytical Chemistry Faculty of Science Nagoya University
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Tanaka Motoharu
Laboratory of Analytical Chemistry, Faculty of Science, Nagoya University
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Ishihara Koji
Laboratory of Analytical Chemistry, Faculty of Science, Nagoya University
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Ishii Masao
Laboratory of Analytical Chemistry, Faculty of Science, Nagoya University
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