Organo-f element Chemistry: Integrated Synthetic, Mechanistic, and Catalytic and Thermochemical Studies

Northwestern University, Evanston IL

Investigators

Abstract

With this award, the Chemical Catalysis Program in the Chemistry Division is funding Dr. Tobin Marks of Northwestern University to discover, understand, and optimize chemical transformations involving metal catalysts. Such processes are of central importance to the chemical enterprise and include efficient, atom-economical, and sustainable catalytic processes for producing fuels, plastics, pharmaceuticals, and other economically important chemicals. This project involves four interlinked focus areas that integrate research and education, and deal with fundamental and technologically-oriented aspects of new catalytic reactions utilizing earth-abundant metal catalysts. Computational analysis is being used to understand the catalytic transformations, and most importantly, to discover new ones. A parallel goal being accomplished is the elucidation of principals for new, efficient, useful, atom-efficient, and environmentally "green" catalytic processes. Participation in this multifaceted/multidisciplinary project, including interactions with industrial scientists, is preparing students with diverse backgrounds for careers in industry, government laboratories, and academia. Professor Marks is studying four research areas: 1) Catalytic hydroelementation to discover, characterize, and understand atom-efficient processes that mediate heteroelement-hydrogen additions to carbon-carbon saturation. This project is focusing on unexplored, lanthanide-catalyzed processes that couple multiple catalytic bond-forming events (cascades), that utilize unsaturated heterocycles (dearomatization), that invent new ways to form oxygen-carbon and sulfur-carbon bonds, and provide actinide catalysts which mediate new bond-forming sequences. 2) Electrophilic catalysis in polar media to study hydroelementation and its reverse using recyclable, highly electrophilic lanthanide catalysts in non-volatile, recyclable ionic liquids or other polar solvents to effect new hydroelementation processes and to develop catalytic reactions that, when coupled to hydrogenation, achieve the microscopic reverse: cleaving carbon-oxygen, carbon-nitrogen, and carbon-sulfur bonds with hydrogen. This research has implications for more efficient processing of sustainable biofuels and other natural resources. 3) Catalytic materials synthesis to use lanthanide, actinide, and related transition metal catalysts in investigating the coupling of olefin polymerization processes with hydroelementation, to produce heteroatom-functionalized polymers, thereby introducing polar functionality at polymer chain ends. 4) Multinuclear catalysis to alter the course of catalytic polymerization and copolymerization reactions by poising two catalytic centers in close proximity. Ideally, such cooperativity effects are likely to alter both the rates and selectivities of kinetic events that control polymer architecture, mechanical properties, and processing characteristics.