Stereoelectronic Effects and Reactivity: Lone Pairs, Hydrogen Bonding, and Proton Transfer

点击翻译按钮获取中文摘要

With support from the Organic Dynamics Program, Dr. Perrin will utilize nuclear magnetic resonance (NMR) spectroscopy to investigate five separate problems: (i) The stereochemistry of amidinate anions will be studied to complete previous investigations of proton exchange in amides and amidines. (ii) Stereoelectronic control phenomena will be studied by evaluating the effect on reactivity of having one or two lone electron pairs antiperiplanar to a leaving group or incoming nucleophile. (iii) The Method of Isotopic Perturbation of Equilibrium will be utilized as a means to investigate the symmetry of the hydrogen bond. (iv) The extent of solvation of ions in aqueous media will be probed by measuring the effect that these ions have upon bond rotation rates. (v) The phenomenon of large secondary kinetic isotope effects will be studied via examination of bond rotations in amides. %%% Applications of modern nuclear magnetic resonance (NMR) techniques have led to increased understanding of molecular structure and reactivity. Dr. Perrin's research program is designed to take advantage of these new techniques in order to study two of the simplest structural elements in organic molecules, i.e., protons and electron pairs. Five projects will be undertaken in an effort to elucidate the nature of such fundamental phenomena as hydrogen bonding and stuructural/conformational effects on reactivity. The results are likely to be of interest to physical-organic chemists, biochemists, and theoretical chemists.