Theory and Design of Transition-Metal Heterodinuclear and Homodinuclear Catalytic Reactions

Brigham Young University, Provo UT

Investigators

Abstract

Developing new catalysts is essential to discovering new chemical reactions. Traditionally, molecular catalysts use one metal atom. Catalysts with two metal atoms (dinuclear) have significant promise for new reactivity, especially for many challenging chemical reactions not yet solved by the classic one metal strategy. Currently, scientists do not completely understand how dinuclear catalysts operate, or how they can be improved. In this project Dr. Daniel Ess of Brigham Young University is using computational methods to understand mechanisms and develop general principles of dinuclear metal-metal interactions. This work, combined tightly with experimental collaboration, is leading to the discovery of new catalysts and chemical reactions. This work also provides scientific training at the interface of chemistry and computer science for graduate and undergraduate students. Dr. Ess is engaged in several outreach activities related to this research. For example, each year Dr. Ess directs a summer chemistry camp at BYU for more than 100 children and youth ages 9-14 with significant participation from underrepresented groups. With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Ess of Brigham Young University is using computational chemistry methods to develop understanding of transition-metal heterodinuclear and homodinuclear catalysis. Catalysts being investigated have a single covalent bond or direct dative/electrostatic interaction between two transition metals or a transition metal and main-group metal. Reaction mechanisms are being investigated for cobalt-zirconium, ruthenium-silver, dinickel, and dirhodium catalysts used in reactions such as carbon-carbon couplings, alkyne hydrogenation, and arene amination. Dinuclear catalyst principles of reactivity and selectivity are being developed by comparing dinuclear versus mononuclear catalysts, and the impact of metal-metal pairing, for ruthenium-zirconium, ruthenium-silver, rhodium-lithium, and nickel-sodium catalysts for reactions such as ethylene polymerization and diene hydroarylation. This work is also using computational methods to design new heterodinuclear catalysts for arene borylation and chiral allylic amination. Undergraduate and graduate students are being trained in modern computational techniques that include using and developing software for spin crossover reactions and direct dynamics. Students interact with experimental groups and are learning how to interface computational chemistry with experiment. Dr. Ess directs a summer chemistry and biochemistry camp using undergraduate labs at BYU for more than 100 children and youth ages 9-14 with significant participation from underrepresented groups. 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.