New Reactions for Utilizing N and P Atoms Derived Directly from the Elements

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Dr. Christopher C. Cummins, Chemistry Department, Massachusetts Institute of Technology, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for the development of new reactions that utilize nitrogen and phosphorus atoms derived directly from the elements. Using complexes in which a nitrogen or phosphorus is triply bonded to a niobium or molybdenum, triple-bond metathesis will be developed as a synthetic route to organic nitrogen and phosphorus compounds. Targets include phosphaalkynes, nitriles, and acylimido compounds. The metal complexes also will be explored as carbene trapping reagents that can undergo beta-elimination to produce species including nitriles. Based on these results, catalytic and stoichiometric systems that react with elemental nitrogen and/or phosphorus to form metal-nitrido or -phosphido complexes that will undergo synthetically valuable reactions will be prepared. This chemistry will be extended to catalytic and stoichiometric reactions of metal-carbon triple bonds. One objective is to explore molybdenum-carbon triple bond chemistry as applied to the synthesis of molecules containing the enediyne functionality.The most abundant element in the earth's atmosphere is nitrogen. While nature is able to utilize atmospheric nitrogen in biological systems, modern chemical science is still seeking technologies for the economical usage of elemental nitrogen. This project grows from the recent discovery of molybdenum and niobium compounds that can cleave the nitrogen-nitrogen bond in dinitrogen under mild conditions. In order to utilize this chemistry, the nitrogen atoms derived from metal assisted dinitrogen cleavage will be used to prepare organic nitrogen compounds. In addition, related processes will be devised to use phosphorus atoms derived from elemental phosphorus. These results will result in new ways to prepare important classes of organic phosphorus and nitrogen compounds. In addition to the scientific results, this project will provide training to a diverse group of undergraduate, graduate, postdoctoral, and visiting senior scientists.