With the support of the Chemical Synthesis Program in the Division of Chemistry, Thomas Gianetti of the University of Arizona and his research group are developing ways to make stable carbocations ? organic molecules that have a positive charge on a carbon atom ? that are attached to electron-rich groups and can serve as catalysts, or ligands for transition metal centers, with dual functionalities. These compounds are being studied to determine if they provide greater tunability and tolerance than more traditional systems that use electron-deficient boron centers instead of carbocations. In addition, Dr. Gianetti and his research team are testing these ambiphilic carbocations as ligands for transition metal complexes to work synergistically with the metal center to activate small molecules toward new modalities for bond formation. These studies will also provide new ways for organic chemists to make value-added compounds and are expected to provide fundamental insight into how these new carbocationic compounds can be used to access new chemical space to support of synthetic chemistry. Dr. Gianetti is also committed to improving communication between scientists and policymakers and is developing a joint course with the College of Law to build a cohort of undergraduate students that can discuss environmental policy across disciplinary barriers. While the physical organic properties of carbocations have been carefully studied, little is known about the use of these compounds as catalysts and ligands for transition metal catalysts in synthetic chemistry. Thomas Gianetti and his research team are developing carbocationic frustrated Lewis pairs and testing their reactivity for nucleophilic additions to paraformaldehyde and alkenes. In addition, helically chiral analogues of these catalysts will be prepared and investigated for catalytic asymmetric transformations. Incorporation of these ambiphilic carbocations into ligand scaffolds is to be further explored to support the cooperative activation of small molecules such as allylic alcohols and NO2. These activities will synergistically provide important training in synthetic chemistry and organometallic concepts for a diverse group of graduate and undergraduate students at the University of Arizona. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.