Oxometal Complexes and Redox Chemistry

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The focus of this research is the use of polyoxometalates and other inorganic oxometal species, which are themselves resistant to oxidation, to catalyze redox transformations of organic compounds of low reactivity, such as alkanes. The immediate goals are to establish the origins of the stability of these catalytic hydrocarbon functionalization systems and to determine the mechanistic and structure-reactivity features of these processes by kinetics, spectroscopic and structural studies. These new polyoxometalate-based catalytic photochemical processes are of potential utility with respect to not only alkane functionalization but also the conversion and storage of radiant energy. The work should lead to improvements in the existing processes, delineation of new spectroscopic phenomena, and development of new catalytic processes. There have been two types of homogeneous catalytic hydrocarbon functionalization processes based on polyoxometalates. The first involves the photochemical functionalization of alkanes, and coupling potentially useful synthetic transformations with the simultaneous conversion of light into chemical energy. The second involves the thermal transfer of oxo and related groups into hydrocarbons. The physical, photochemical and photophysical attributes of several recently documented interactions between various classes of organic substrates and polyoxometalates will be probed by picosecond and other spectroscopic studies, X-ray crystallography and photochemical experiments.These experiments are expected to yield further information on the potential applications of soluble oxometal species to redox transformations of organic and inorganic molecules.