With this renewal award, the Organic and Macromolecular Chemistry Program continues its support of the work of Professor Albert J. Fry of the Department of Chemistry at Wesleyan University in Middletown, CT. The research will extend the PI's investigations of physical organic electrochemistry. The anodic oxidation and the chemical reactions of organosilanes and related substances will be studied. Compounds containing silicon, which is just below carbon in the periodic table and more electropositive than carbon, readily give up an electron to a negative electrode. A second group within the same molecule such as a remote phenyl ring can assist this electron transfer. This research will explore the dimensions of this "remote effect" in order to determine what other groups facilitate electron transfer and to evaluate the possibility of replacing silicon with another element in order to discover additional synthetically useful reactions. These investigations will be complemented by computational studies aimed at developing methods for accurate estimation of the redox potentials of organic substrates and determining the nature and stereochemistry of ion-pairing and other interactions between organic cations and anions in solution.
A diverse, multiracial group that includes both graduate and undergraduate students will carry out this research. The project will train students in the important areas of electrochemistry, synthesis, and computational chemistry. This research is expected to have broad positive impact on mechanistic and synthetic electrochemistry and on the development of catalysts with unique redox properties.
