Steric Modulation of Electronic Effects

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This grant from the Organic Dynamics Program supports the continuing work of Professor Joseph B. Lambert at Northwestern University, who will study stereoelectronic aspects of reactive intermediates. One focal point is to determine how electronic effects are propagated through sigma bonds. Targets are to evaluate the zeta effect of stannylenium ions, the mechanism of the beta- silicon effect, and a search for the beta-phosphonate effect in carbocation formation. The second focal point is to obtain new formulations of solvents and anions to produce free silyl, germyl, and stannyl cations. The third topic concerns conformations of flexible molecules in the solid state, which is footed on five- membered rings and the use of a cultivated solid state NMR spectroscopic technique. %%% The results from Professor Joseph B. Lambert's studies on reactive intermediates will contribute to our understanding on how electronic effects are propagated through bonds. His research is focussed largely on silyl and stannyl cations. Their isolation is also sought to verify their existence as intermediates. These mechanistic studies have the potential to translate in a broad spectrum of synthetic applications. Novel conformational studies on cyclopentanes will be conducted that will provide information that is relevant in the area of molecular dynamics.//