CAREER: CAS: Modulating Ligand-based C-H and N-H Bond Strengths for Sustainable Synthesis and Catalysis

With funding from the Chemical Catalysis and Chemical Mechanism, Function, and Properties Programs of the Division of Chemistry, Dr. Prokopchuk at Rutgers University-Newark will design redox-active organic and organometallic systems capable of transferring protons, electrons, and hydrogen atoms in a sustainable and efficient manner. The controlled delivery of hydrogen is essential for preparing fuels, life-saving medicines, and industrial-scale chemical feedstocks.

To deliver hydrogen sustainably and efficiently, there is a need to understand the energetic requirements for transferring hydrogen from organic molecules containing carbon-hydrogen (C-H) and nitrogen-hydrogen (N-H) bonds. Dr. Prokopchuk will also educate student cohorts at the high school and undergraduate levels about the underlying chemical properties of scientific glassware, with a special focus on the importance of glassware in chemistry.

This outreach effort will involve hands-on workshops at a local non-profit organization that specializes in glassblowing education, giving students a well-rounded experience by delving into glass and its remarkable chemical properties.

Dr. Prokopchuk and his laboratory at Rutgers University-Newark will design redox-active organic and organometallic systems capable of transferring protons, electrons, and hydrogen atoms in a sustainable and efficient manner, impacting several key areas of synthesis and catalysis. The unifying theme will be to understand how ligand-based L-H scaffolds can efficiently manage H atom inventories in cooperation with redox-active chemical moieties.

To this end, Dr. Prokopchuk and his laboratory will (1) measure C(sp3)-H bond thermochemistries of diamondoid pincer complexes for applications in sustainable C-H functionalization reactions; (2) efficiently synthesize value-added molecules via proton-coupled electron transfer (PCET) electrocatalysis using amine-rich cyclopentadienyl complexes; and (3) modulate N-H and C-H bond strengths to perform novel PCET reactions.

These tasks will be accomplished with a strong focus on mechanistic analysis via experiment and computation to rationally modulate ligand-based L-H bond strengths. Critical aspects of sustainability are preserved by using Earth-abundant metals, thereby maximizing the potential for transformative impact. The proposed projects will contribute to the activity, selectivity, and energy efficiency of catalytic processes that are important to the research and commodity chemical industries.

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.