This project, funded by the Inorganic, Bioinorganic and Organometallic Chemistry Program, will support the continuation of studies by Professor Patricia A. Shapley, of the University of Illinois, into the organometallic chemistry of the iron triad. A major area for consideration is the chemistry of alkyl-imido-cyclopentadienylosmium(VI) and -ruthenium(VI) complexes, which transfer the imido group to organic substrates. Attempts will be made to synthesis oxo and sulfido analogs that will also react with organic substrates to transfer these groups. A secondary objective of this phase of the work is to make these reactions catalytic and/or chiral. Chiral forms of heteronuclear species formed from a dialkyl nitridoosmium complex and chromate ion, which was earlier found to oxidize primary and secondary alcohols, have recently been synthesized. Attempts will be made to resolve these complexes and study their effectiveness as reagents for chiral resolution of secondary alcohols. A third area to be considered is the preparation and study of high oxidation state alkyl iron (III/IV) complexes, and neutral oxo iron(IV) complexes. The former will be generated by chemical or electrochemical oxidation of known alkyliron(II) complexes and the latter from reduction of the ferrate anion. Some examples of oxoiron(IV) complexes that are soluble in organic solvents are already available. This project has as its primary objective the acquisition of a fundamental understanding of the chemical reactivity of several new classes of organometallic compounds that contain one of the elements from the iron family. Whereas the specific objectives are to understand the factors that determine the stability and reactivity of these compounds, there is considerable potential for the development of reagents that have applications in the synthesis of organic compounds. This may ultimately provide for better ways to synthesize known biologically active compounds, or to prepare new ones.
