Transactions of the Faraday Society
Transactions of the Faraday Society was published from 1905 - 1971.
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Paper
Trans. Faraday Soc. , 1971, 67, 110 - 118, DOI: 10.1039/TF9716700110
Kinetics of proton and deuteron transfer reactions of 4-nitrophenylnitromethane with triethylamine and tri-n-butylamine in acetonitrile solvent
E. F. Caldin, A. Jarczewski and K. T. Leffek
The second-order rate constants for the proton and deuteron transfer reactions between 4-nitro-phenylnitromethane and the organic bases triethylamine and tri-n-butylamine have been determined at eight different temperatures between 0 and 35°C, using the stopped-flow technique. The four reactions are characterized by low enthalpies of activation and large negative entropies of activation. The isotope effects give values for (
D
D–HH) of 1.02 and 0.74 kcal mol–1 and (SD–SH) of 1.2 and 0.9 cal mol–1 K–1 for triethylamine and tri-n-butylamine respectively. The rate ratios are small for primary deuterium effects; kH/kD for Et3N at 0°C is 3.56 and for n-Bu3N at 0°C is 2.41. These reaction constants are used to elucidate the type of energy barrier involved in the reaction and the nature of the transition state.
