Abstract
Changes in the hybrid state of atomic orbitals of nitrogen and p-character of LEP, which occur under the effect of saturated hydrocarbon radicals and polar substituents in aliphatic amines, differ substantially. Therefore, the effect of the both substituents on the basicity constants of amines cannot be described by the single formal type of interaction. The “anomalous” changes in the basicity in the series of primary, secondary, and tertiary alkylamines, which are discussed in the literature, and the correlations pK BH+ = f(∑σ*) and ΔG B = f(∑σ*) are, in fact, imaginary, because the alkyl radicals at the N atom do not manifest the electron-donor properties.
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Korzhenevskaya, N.G., Rybachenko, V.I. & Kovalenko, V.V. Peculiarities of the effect of the electronic nature of substituents on the basic properties of aliphatic amines. Russian Chemical Bulletin 52, 893–899 (2003). https://doi.org/10.1023/A:1024496225076
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DOI: https://doi.org/10.1023/A:1024496225076