Ligand Enhancement of Transition Metal Reactivity

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Dr. Kenneth G. Caulton, Chemistry Department, Indiana University, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program of the Chemistry Divison to utilize the [(R2PCH2SiMe2)2N]-1 (PNP) ligand to develop atom transfer reactions to and from metals coordinated to it. Work proposed includes transfer of atoms to highly reduced (PNP)M or from rare examples of (PNP)MG where G may be O or N. Properties of the complexes, such as spin state, bond order, chemical bond-type and location of empty orbitals and of lone pairs, will be studied for their influence on chemical reactivity. Comparative studies down the Fe - Ru - Os group and across the Fe - Co - Ni series will be conducted to establish periodic trends. In particular, the first transition series metal complexes are expected to react more rapidly than heavier element analogs and possess special freedom to employ 1-electron steps.The chemistry to be studied will develop a basic understanding of fundamental organometallic chemistry. The education of undergraduate, graduate, and postdoctoral students will be an important contribution of this project.