Position-Specific Secondary Deuterium Isotope Effects on Basicity of Pyridine

被引:22
|
作者
Perrin, Charles L. [1 ]
Karri, Phaneendrasai [1 ]
机构
[1] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA
基金
美国国家科学基金会;
关键词
KINETIC ISOTOPE; PROTON-TRANSFER; MECHANISM; CONSTANTS; EXCHANGE; SPECTRA; STATE;
D O I
10.1021/ja105331g
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Secondary isotope effects (IEs) on basicities of various deuterated pyridine isotopologues and of 2,6-lutidine-2,6-(CD3)(2) have been accurately measured in aqueous solution by an NMR titration method applicable to a mixture. Deuteration at any position of pyridine increases the basicity, but the IE per deuterium is largest for substitution at the 3-position and smallest for the 2-position, which is closest to the site of N-protonation, smaller even than that for 2-CD3 substitution. Computations at the B3LYP/cc-pVTZ level overestimate the magnitude of the measured IEs but largely reproduce the variability with isotopic position. Because the calculated IEs are based on changes in vibrational frequencies on N-protonation, the correspondence between calculated and experimental IEs implies that they arise from zero-point energies, rather than from inductive effects.
引用
收藏
页码:12145 / 12149
页数:5
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