This CAREER award by the Inorganic, Bioinorganic and Organometallic Chemistry program supports work by Professor Peter Zhang at University of Tennessee Knoxville to study catalytic reactivities of metalloporphyrins for carbene and nitrene transfer reactions. In contrast to oxotransfer reactions, the analogous carbene and nitrene transfers by metalloporphyrins are less developed, but are important both fundamentally and practically. They generate valuable insights that aid the understanding of related biochemical processes and provide models for approaches to convert inexpensive and abundant hydrocarbons into value-added functional molecules via C-C and C-N bond formations. New porphyrins with tunable electronic, steric, and chiral environments will be synthesized by a modular approach from readily available bromoporphyrin synthons and will be used as supporting ligands to systematically probe, control, and optimize the catalytic reactivities and selectivities of metalloporphyrins. Detailed mechanistic studies, including elucidation of putative metalloporphyrin-carbene and -nitrene intermediates, will be carried out to understand the origin of catalytic reactivity and selectivity of metalloporphyrins. It is hoped that practical catalytic systems based on metalloporphyrins will ultimately be developed for selective conversions of alkenes and alkanes into more valuable functional molecules via well-defined carbene and nitrene transfer processes.
The multidisciplinary nature of the proposed research program provides an edcational opportunity for students to solve fundamentally and practically important scientific problems through a combination of inorganic, organic, organometallic, and biomimetic approaches. The proposed research will be integrated with a range of education missions. First, focused efforts will be made to mentor undergraduate students in active research projects, especially for women, underrepresented minorities, and students from primarily undergraduate institutes (PUIs), attracting them into careers in chemical and related sciences. Second, arrangements will be made to sponsor faculty members at PUIs to conduct research projects in the PI's laboratory, enhancing their research and educational opportunities. Third, an educational component titled "The Colors of Life", which is related to the proposed research, will be developed for K-12 teachers/students and the general public, promoting their appreciation of and interests in chemical science.
