RUI: Rearrangements of Relaxed and Excited Carbenes.

University Of Hawaii, Honolulu

Investigators

Abstract

With joint support from the Chemical Mechanism, Function, and Properties (CMFP) Program of the Chemistry Division and the Established Program to Stimulate Competitive Research (EPSCoR), Professor Matthew Platz at the University of Hawai’i-Hilo (UHH) will carry out research with undergraduate students in the areas of organic synthesis, photochemistry, chemical analysis of reaction product mixtures, and computational modeling. This research will test advanced theoretical predictions of a new photochemical reaction mechanism that involves divalent carbon intermediates known as carbenes. UHH consistently ranks among the most diverse four-year campuses in the nation. About half of all UH Hilo undergraduates are Pell eligible, and almost two thirds take fewer than 15 credit hours per semester. This project will provide the opportunity for a modern research experience to economically challenged students from historically underrepresented populations. The project will strengthen collaboration between faculty and students at UH Hilo and The Ohio State University. UHH students will carry out research at Ohio State during the summer months, gaining valuable hands-on experience with state-of-the-art instrumentation. In Hilo, Hawai’i, students will synthesize diazirines, diazo compounds and oxadiazolines as carbene precursors, expose these compounds to monochromatic UV-vis radiation in acetonitrile/methanol mixtures, and analyze the Z/E ratio of alkene and ether products so produced as a function of excitation wavelength and methanol concentration. The predictions of theory in regard to carbene reactivity will be confirmed if the Z/E ratio of alkenes changes dramatically once a critical energy of exciting photons is reached. UHH undergraduates will spend summer months at the Ohio State University, an R1 university, developing their skills in computational chemistry under the tutelage of Professor Christopher Hadad, an expert in the field. The students will also participate in femtosecond time-resolved IR experiments measuring the lifetimes and reactivities of carbenes in collaboration with Professor Claudia Turro at the Ohio State Center for Chemical and Biophysical Dynamics. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.