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2164 Journal of the American Chemical Society 1 102:7 1 March 26, 1980 Is There a Nitroalkane Anomaly?
 

Summary: 2164 Journal of the American Chemical Society 1 102:7 1 March 26, 1980
Is There a Nitroalkane Anomaly?
Noam Agmon
Contributionfrom the Department of Physical Chemistry, The Hebrew University,
Jerusalem, Israel. Received June 28, I979
Abstract: The abnormal Brfnsted slopes observed for nitroalkanes are interpretedas a variation in the work terms, which is
caused by a variation in hydrogen bond strengthswith the free energy for proton transfer,rather than as an anomaly in the pro-
ton-transferstage itself.
I. Introduction
For most seriesof related proton-transfer reactionsi the rate
constant, k , is found to correlate with the equilibrium constant,
Keq.The Brpnsted slope
a! d In k l d In K,, (1)
varies in the range zero (for very exothermic reactions) to one
(for very endothermic reactions). These findingsmotivated the
postulate^^^^ that a is a measure of the positionof the transition
state along the reaction coordinate,2 which is early for exo-
thermic and late for endothermic reaction^.^ However, in some
series of nitroalkanes a! outside the range 0-1 was found," and
the validity of the Leffler-Hamm~nd~.~postulates was ques-

  

Source: Agmon, Noam - Institute of Chemistry, Hebrew University of Jerusalem

 

Collections: Chemistry