CAREER: CAS: Vanadium-Based Alkyne Metathesis

With the funding from the Chemical Catalysis Program of the Division of Chemistry, Dr. Bukhryakov of Florida International Univ will use an Earth-abundant first-row metal, vanadium, to develop catalysts for alkyne metathesis. Alkyne metathesis is a widely used synthetic method for the synthesis of chemicals containing carbon-carbon triple bonds, including advanced materials that have potential applications in organic light-emitted diodes, organic photovoltaics, organic field-effect transistors, and optical and molecular sensors. In addition, alkynes are essential starting points for producing a large variety of organic compounds, taking advantage of the chemical versatility of a triple bond. While the current alkyne metathesis chemistry exclusively relies on second- and third-row transition metals, this project focuses on earth-abundant first-row metal vanadium. This, in turn, will make essential chemicals more accessible to consumers and decrease the human environmental footprint. The proposed educational plan will focus on the research engagement of high-school and undergraduate students from underrepresented groups. It will include the "Recycle your PET" project, a summer research internship for high-school students, and establishing a research advising office at FIU. The project's ultimate goal is to increase the number of minority students who pursue a doctoral degree in science. The proposed research plan will focus on developing well-defined first-row transition metal catalysts based on V alkylidynes for alkyne metathesis, a transformation that has never been utilized, to offer improved reactivity and provide inexpensive and greener alternatives to existing catalysts. The team will perform a systematic and comprehensive study on the influence of size and the electronic characteristics of the ligand set in V-based catalysts on the alkyne metathesis. The proposed investigations will identify the crucial factors required for efficient, reliable, and selective V-catalyzed alkyne metathesis of a wide variety of olefins. The long-standing goal of the proposed research is implementing V-catalysts for alkyne metathesis in academia and industry, which will be achieved in three steps: 1) Catalysts development based on a comprehensive study of the influence of neutral and anionic ligands on the catalyst activity, selectivity, and stability; 2) Mechanistic investigation using kinetic studies of initiation, productive metathesis, and decomposition steps. 3) Applications of V-based alkyne metathesis to complement existing transformations and offer a distinct reactivity. The research program will aid to prepare the next generation of scientists and take a leadership role in ongoing efforts to revolutionize organic, organometallic, polymer chemistry, and catalysis for a sustainable future. 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.