CAREER: Computational and Experimental Mechanistic Approach to Iron Catalyst and Reaction Design

Texas A&M University, College Station TX

Investigators

Abstract

In this CAREER project, funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professor Osvaldo Gutierrez of the Department of Chemistry at the University of Maryland College Park is using computational and experimental tools to elucidate the mechanisms of iron-catalyzed carbon bond forming reactions. Carbon bond forming reactions are important in pharmaceutical and other fine chemical products; However, such reactions often require the use of rare and expensive metals. Replacement of the expensive metals in these processes with earth-abundant and non-toxic iron is the goal of this project. In addition to the research activities, Professor Gutierrez is piloting a partnership between the University and the nearby Prince George's Community College to encourage community college students to conduct hands-on summer research at University of Maryland and to train community college faculty to use and implement modern computational tools in undergraduate education. These efforts are further enhanced with the Alliance for Diversity in Science and Engineering. Knowledge of the mechanisms of iron-catalyzed processes is rudimentary, thus hindering rational catalyst design. This hypothesis-driven project focuses on performing mechanistic studies designed to increase understanding of the factors that control reactivity and selectivity. in carbon-bond forming reactions. By performing both calculations and synthesis in one laboratory setting, Professor Osvaldo Gutierrez and his research team are well positioned to address new developments from both the computational or experimental sides of the research to gain a far-reaching picture of the factors controlling product selectivity. Specific research goals include the use quantum mechanical calculations and chemical synthesis of mechanistic probes to elucidate the mechanisms of iron-catalyzed carbon-carbon cross-coupling reactions. The team also seeks to develop predictive models, based on transition state calculations, of reactivity and selectivity of iron-catalyzed carbon-carbon double bond functionalization. The researchers also establish guiding principles for predicting geometry and spin states of diamine bispyridine iron(II) catalysts. This project may lead to foundational catalyst design principles for broader applications in catalytic chemical synthesis. 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.