Browsing by Author "Ozerov, Oleg"

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Applications of Carbon-Fluorine Bond Activation by Main Group Electrophilic Catalysts to PFAS Remediation
Chemistry; TAMU; https://hdl.handle.net/20.500.14641/458; DOD-Navy-Naval Research Laboratory
Significantly fluorinated triarylmethyl cations have long attracted attention as potentially accessible highly reactive carbocations, but their isolation in a convenient form has proved elusive. We show that abstraction of chloride with a cationic silylium reagent leads to the facile formation of di-, tetra-, and hexafluorinated trityl cations, which could be isolated as analytically pure salts with the [HCB11Cl11] counterion and are compatible with (halo)arene solvents. The F6Tr+ cation carrying six meta-F substituents was computationally predicted to possess up to 20% higher hydride affinity than the parent triphenylmethyl cation Tr+. We report that indeed F6Tr+ displays reactivity unmatched by Tr+. F6Tr+ at ambient temperature abstracts hydrides from the C–H bonds in tetraethylsilane, mesitylene, methylcyclohexane, and catalyzes Friedel–Crafts alkylation of arenes with ethylene, while Tr+ does none of these.
New Catalytic Chemistry Based On Borylation Of Alkynes
Chemistry; TAMU; https://hdl.handle.net/20.500.14641/458; National Science Foundation
The Chemical Catalysis Program of the Chemistry Division supports the project by Professor Oleg Ozerov, a faculty member in the Department of Chemistry at Texas A&M University. The work in the Ozerov group straddles the fields of organic and inorganic chemistry. His group is exploring recently discovered catalytic processes to introduce carbon-boron bonds into organic compounds, especially around carbon-carbon triple bonds (alkynes) and double bonds (alkenes). The importance of these borylated compounds is in their versatility as building blocks for more complex organic molecules, with potential applications in the synthesis of pharmaceuticals and new materials. The project benefits from a network of US and international collaborators, including those at primarily undergraduate institutions (PUI). It also serves as a vehicle for broadening participation in the Texas A&M graduate program and educating Texas A&M graduate students about PUI careers and introducing them to secondary school outreach. The primary goal of this project is the exploration of the full potential of dehydrogenative borylation of terminal alkynes (DHBTA) and the reactions derived from it. Successful implementation of the borylation processes of interest requires development of molecular transition metal catalysts in a framework of specifically designed supporting ligands. The project aims to gain fundamental insight into the mechanism of iridium-catalyzed DHBTA and other borylation reactions and the role of the supporting ligand in influencing reaction outcomes. Other goals being investigated include 1) the cyclization reactions of DHBTA products, alkynylboronates, and 2) the potential of the DHBTA-inspired reactivity in catalysis of other C-H borylation reactions. Undergraduate students are involved directly in the Ozerov group and via collaboration with Prof. Larsen at Ithaca College and other PUI faculty. PUI collaborations introduce Texas A&M graduate students to PUI opportunities and careers and draw more undergraduates into research and into graduate education.