This award is made in the Inorganic, Bioinorganic and Organometallic Chemistry Program in support of the research of Craig L. Hill at Emory University. The award provides continued support for Hill's research on hydrocarbon oxidation catalyzed by transition metal polyoxometallates. Both thermal and photochemical systems will be studied. The work will address fundamental problems in the activation and transfer of oxygen from metal centers to C-H bonds and other areas of relevance to both industrial and biological systems. The objectives of the research are: (1) to establish the factors which control product selectivity, catalyst stability, and key mechanistic features in sustained oxo transfer to alkanes catalyzed by homogeneous, very active and stable, oxidatively-resistant inorganic metalloporphyrin analogues (IMAs), (2) to develop chiral IMAs that will catalyze asymmetric hydroxylation of alkanes, (3) to delineate the factors that affect the quantum yields of competing polyoxometallate excited state decay processes and the selectivities and turnover rates in hydrocarbon photooxidation, (4) to convert unactivated C-H bonds into carbonium ions for useful reactions including the catalytic production of monofluorinated hydrocarbons directly from hydrocarbons and fluoride ion, and (5) to rigorously establish the structural, spectroscopic and photochemical properties of polyperoxo(oxo)tungstates that have potential for use as negative inorganic photoresists for microlithography and as selective oxidants for olefins.
