Investigations of the Cage Effect and Aqueous Organometallic Radical Chemistry

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Dr. David R. Tyler, Chemistry Department, University of Oregon, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for studies on the reactivity of organometallic free radicals. As one portion of the investigation the cage effect, i.e. the effect responsible for the greater reactivity of a radical pair in solution than in the gas phase, will be probed. A variety of `cage efficiency factors`, a number that expresses the efficiency of radical cage pair combinations, will be accumulated for a variety of radical pairs which differ in mass, size, and shape. These data will provide predictive understanding of the cage effect. The second part of the project involves an investigation of the reactivity of 17- and 19-electron organometallic species in aqueous solution. New methods for generating water soluble organometallic radicals will be developed and the fundamental reactivity and catalytic properties of the radicals will be systematized. Each electron in a chemical compounds is usually paired with another. However, there are some compounds which contain an unpaired electron. These are called radicals, they often are quite chemically reactive, and there is a growing realization that they are involved in many chemical processes. The object of this project is to uncover the principles which control the chemical behavior of metal containing radicals and to develop radicals which can dissolve in water. Since water is an environmentally friendly solvent, the ability to generate radicals in aqueous solutions will permit reactions which normally must be carried out in organic solvents to be performed in a less polluting medium.