NMR study of the dynamic behaviour of the system 2-ethylhexylsodium-2-ethylhexyllithium in heptane |
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Authors: | S. G. Sakharov N. I. Pakuro A. A. Arest-Yakubovich L. V. Shcheglova P. V. Petrovskii |
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Affiliation: | a N.S. Kurnakov Institute of General and Inorganic Chemistry, RAS, Leninskii pr. 31, 117907 Moscow, Russia;b L.Ya. Karpov Institute of Physical Chemistry, 10 ul. Vorontsovo Pole, 103064 Moscow, Russia;c N.A. Nesmeyanov Institute of Organoelement Compounds, RAS, 28 ul. Vavilova, 117813 Moscow, Russia |
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Abstract: | Mixtures of 2-ethylhexylsodium and 2-ethylhexyllithium are studied by 1H- and 13C-NMR spectroscopy in the temperature range from 20 to −50°C in hydrocarbon solutions. Characteristic temperature-dependent spectra obtained are indicative of dynamic exchange processes taking place in the system. The following activation parameters are found: ΔH≠=31.7±2.7 kJ mol−1; ΔG≠313=58.7±0.6 kJ mol−1; ΔS≠=−86.37±10.8 J mol−1 K−1. The negative value of the activation entropy indicates that the exchange proceeds through the associative mechanism. The participation in exchange reactions of aggregates, containing both sodium and lithium derivatives, is suggested. |
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Keywords: | Alkylsodium Alkyllithium DNMR |
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