Novel M-C Bond Functionalization Reactions in Aqueous and Hydrocarbon Media Involving M(II)/M(IV) Redox Couples (M = Pd, Pt)

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This award to Professor Andrei Vedernikov at the University of Maryland at College Park is to study the reactivity of a number of new organoplatinum(II) and organopalladium(II) compounds that activate alkynes and arylimines with oxygen and hydrogen peroxide in aqueous media. This study focuses on the structure-reactivity relationships for organometallic oxidation and C-X reductive elimination, which are of fundamental importance for developing selective platinum- and palladium-mediated catalytic reactions. The reactivity of some monohydrocarbyl platinum(IV) and monohydrocarbyl palladium(IV) complexes with respect to C-X bond reductive elimination will be characterized in detail in aqueous media, including kinetics studies and DFT modeling. New chelating semilabile ligands will be developed for the catalytic selective aerobic oxidation of olefins and alkynes in aqueous media. A recently discovered catalytic reaction involving Pd- catalyzed CH- hydroxylation of arylimines with hydrogen peroxide, will be subjected to a detailed mechanistic analysis and its substrate scope expanded. The feasibility of new catalytic processes, such as oxidative CH fluorination with O2 as the oxidant and oxidative coupling of ethane and benzene, will also be explored. Knowledge of structure-reactivity relationships for reactions involving oxygen and hydrogen peroxide as oxidants, water as solvent and organopalladium(II) and organoplatinum(II) complexes as substrates will be valuable for the development of new selective and efficient "green" synthetic protocols. An important outcome of this research is the professional training of graduate, undergraduate and high school students. Summer research students from the ACS SEED program and local high schools will be involved. Undergraduate and graduate students from underrepresented groups in Maryland and at the University of Maryland will participate.