Variable-temperature and variable-pressure nitrogen-14 NMR studies on the exchange reaction of different nitriles at the nickel(II) ion.
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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变温变压氮 14 NMR 研究不同腈在镍 (II) 离子上的交换反应。
DOI：
10.1246/bcsj.62.1852
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发表时间：
1989
影响因子：
4
通讯作者：
Motoharu Tanaka
中科院分区：
文献类型：
--
作者：
M. Ishii;S. Funahashi;K. Ishihara;Motoharu Tanaka
本文用~（14）N NMR谱线展宽法测定了三氟甲磺酸镍溶液中几种腈与镍离子交换反应的活化参数。活化焓值（ΔH\eweq/kJ mol−1），活化熵（ΔS\eweq/J mol-1 K-1），以及零压力下的活化体积（ΔV0\eweq/cm 3 mol−1）分别为：乙腈41.4±0.5、−30±2和+12.0 0. 4;丙腈42.0±0.4、−25±2和+13.7 0. 5;丁腈为43.3±0.7、−23±2和+13.1 0. 5;异丁腈为43.3±0.5、−19±2和+12.4 0. 6;戊腈为47.1±1.2、−10±4和+14.4 0. 4;苄腈为51.6±1.9、+4 6和+13.1 0. 6。尽管腈的摩尔体积变化很大，但活化体积变化很小。在此基础上，计算了腈分子取向的活化能（EQ/kJ mol−1）和零压活化体积（ΔVq\eweq cm 3 mol−1）。
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 14N NMR line broadening method at various temperatures and pressures up to 220 MPa. Values of activation enthalpy (ΔH\eweq/kJ mol−1), activation entropy (ΔS\eweq/J mol−1 K−1), and activation volume at zero pressure (ΔV0\eweq/cm3 mol−1) 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 (EQ/kJ mol−1) and the activation volume at zero pressure (ΔVq\eweq cm3 mol−1) for the reorientation of nitrile mole...