Grant: Research Tools and Instruments - Category 1 (<$150,000)

Radicals are key intermediates in a number of chemical transformations and their reactivity involves two key steps: 1. Radical formation via breaking of a chemical bond, A-B, to give two highly reactive radical species A(dot) and B(dot). This step occurs spontaneously or through the application of energy in the form of heat or light; 2. Termination of the reaction and this involves the formation of a bond between two similar or dissimilar radicals, A(dot) + B(dot) to give A-B. Most of these radical reactions involve transient species. In contrast, there are some known radicals that are stable enough to be placed in a bottle on the shelf. Unfortunately, because of their stability, many of these species are not reactive enough to participate in a number of chemical transformations. However, there are a handful of compounds that contain weak or strained bonds in the solid state that either partially or fully dissociate in solution through breaking of the element-element bond. These form persistent radicals--i.e. a radical that has a very long lifetime, but is not "bottle-able". In the proposed research, our research group will be studying the reactivity of these persistent, phosphorus-based radicals that have intermediate stability. Their reactivity with common small molecules will be investigated and compared and contrasted to that of chlorine, bromine and other common radical forming species. Once reactivity trends have been established, new, metal-based radicals (such as aluminum) will be investigated.These studies will further the understanding of radical reactivity which may have implications in fundamental science or industry/pharmaceuticals. Research will be carried out by a combination of masters and undergraduate students. This research will provide training, combining both theory and practical skills, that will be beneficial to the student for future prospects in graduate/professional school or in chemical industry. An inert atmosphere glovebox is essential for the synthesis of these sensitive sensitive compounds and the success of my research program.