Long & Medium-Term Research: Activation and Functionalization of Chlorocarbons This award recommendation is made under the Program for Long & Medium-Term Research at Foreign Centers of Excellence. The program seeks to enable U.S. scientists and engineers to conduct long-term research abroad at research institutions of proven excellence. Awards provide opportunities for the conduct of joint research, and the use of unique or compli- mentary facilities, expertise and experimental conditions in foreign countries. This award for a proposal sponsored by Dr. David A. Hoffman of Harvard University will support a twelve-month visit to France by Dr. Derk A. Wierda to work with Professeur John A. Osborn of the Institut Le Bel of the Universit Louis Pasteur in Strasbourg on "Activation and Functionalization of Chlorocarbons." Chlorocarbons form a relatively inert class of compounds with properties which can be useful, such as solvent, or noxious, such as chlorinated aromatics (PCBs). It has recently been discovered that a series of complexes of Pd(0) will activate C-Cl bonds under mild conditions. Such complexes also serve as catalysts for the carbonylation of CH2Cl2 and C6H5Cl. The original work into chlorocarbon activation will be extended to other chloro- and polychloro- containing compounds. The researchers will conduct mechanistic studies to better understand how the process of chlorocarbon activation occurs. The will perform further research into potential catalytics reactions involving these systems. One possible reaction of interest is hydrodechlorination, a process by which chlorocarbons would be transformed into hydrocarbons. Reaction of CH2Cl2 in the presence of CO, H2, base and palladium complex catalytically generates ketene, a very reactive organic molecule. The researchers will investigate this process in the presence of various ketene traps. They will examine generation of other ketenes in situ. They shall perform investigations into the possibility of breaking the much stronger C-F bonds by similar methods. The award recommendation provides funds to cover, as appropriate, international travel, local travel abroad, stipend, dependents' allowance if applicable, and a flat administrative allowance of $250 for the U.S. home institution.
