Development of Ruthenium(II) based Hydroarylation Catalysts Supported by Phosphorus-based Ligands and 4,4′-Di-tert-butyl-2,2′-dipyridyl.
Location
Poster Sessions (Learning Commons)
Session Format
Poster Presentation
Your Campus
Armstrong Campus - Armstrong Center, April 19th
Academic Unit
Department of Chemistry
Research Area Topic:
Natural & Physical Sciences - Chemistry
Co-Presenters and Faculty Mentors or Advisors
Dr. Brandon Quillian (Advisor)
Abstract
Many of the current petroleum processing technologies were developed more than a century ago. While very reliable methods to produce alkylarenes, they produce an immense amount of hazardous chemical waste and are energy intensive. To make a better and “greener” method, we are examining a class of ruthenium catalysts that may benefit from the qualities of its supporting environment.The ruthenium-carbon bond is a highly active entity that has been implicated in stoichiometric and catalytic applications. Phenylations of ruthenium often occur via metathesis reactions between a ruthenium-halide and highly nucleophilic phenylmagnesium and phenyllithium reagents. The success of the phenylation often depends on the substrate and/or halide identity. Ru-Cl bonds are commonly utilized in such reactions due to the commercial availability of starting materials. We have begun investigating the phenylation para-cymene ruthenium diiodide complexes supported by phosphorus ligands, (p-cymene)RuI2(PR3), to examine how the phosphorus ligand influences the reaction. Four (p-cymene)RuI2(PR3) complexes (PR3= P{OCH2}3CEt, 1; PMe3, 2; P(OMe3), 3 and PPh3, 4} were prepared by reacting [p-cyemeneRuI(μ-I)]2 with the respective phosphorus ligands. In a previous study, it was found that (p-cymene)RuI2(P{OCH2}3CEt) (1) could be rapidly and cleanly phenylated with commercially available phenylmagnesium bromide to yield (p-cymene)RuI(Ph)(P{OCH2}3CEt) in good yield. To test the scope of this reaction, complexes 2-4 were phenylated under similar conditions as that of 1, which showed complete conversion to their respective (p-cymene)RuI(Ph)PR3 complex (PMe3 = 5, P(OMe3) = 6 and PPh3 = 7). Compounds 2-7 were characterized 1H, 13C, and 31P NMR spectroscopy and complexes 2, 5, and 6 were also characterized by single crystal X-ray diffraction studies. In addition, the stabilities of 5-7 were examined, which revealed complex 5 and 6 are highly sensitive to air and moisture, while 7 is quite stable for days when stored in air. Presented herein is the synthesis, characterization, and reactivity of these complexes.
Program Description
The synthesis, characterization, reactivity and properties of ruthenium-based compounds as potential catalysts for the conversion of petroleum-based products into value-added molecules will be discussed.
Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 License.
Presentation Type and Release Option
Presentation (File Not Available for Download)
Start Date
4-19-2022 1:00 PM
End Date
4-19-2022 2:00 PM
Recommended Citation
Cartrette, Katelyn, "Development of Ruthenium(II) based Hydroarylation Catalysts Supported by Phosphorus-based Ligands and 4,4′-Di-tert-butyl-2,2′-dipyridyl." (2022). GS4 Georgia Southern Student Scholars Symposium. 19.
https://digitalcommons.georgiasouthern.edu/research_symposium/2022A/2022A/19
Development of Ruthenium(II) based Hydroarylation Catalysts Supported by Phosphorus-based Ligands and 4,4′-Di-tert-butyl-2,2′-dipyridyl.
Poster Sessions (Learning Commons)
Many of the current petroleum processing technologies were developed more than a century ago. While very reliable methods to produce alkylarenes, they produce an immense amount of hazardous chemical waste and are energy intensive. To make a better and “greener” method, we are examining a class of ruthenium catalysts that may benefit from the qualities of its supporting environment.The ruthenium-carbon bond is a highly active entity that has been implicated in stoichiometric and catalytic applications. Phenylations of ruthenium often occur via metathesis reactions between a ruthenium-halide and highly nucleophilic phenylmagnesium and phenyllithium reagents. The success of the phenylation often depends on the substrate and/or halide identity. Ru-Cl bonds are commonly utilized in such reactions due to the commercial availability of starting materials. We have begun investigating the phenylation para-cymene ruthenium diiodide complexes supported by phosphorus ligands, (p-cymene)RuI2(PR3), to examine how the phosphorus ligand influences the reaction. Four (p-cymene)RuI2(PR3) complexes (PR3= P{OCH2}3CEt, 1; PMe3, 2; P(OMe3), 3 and PPh3, 4} were prepared by reacting [p-cyemeneRuI(μ-I)]2 with the respective phosphorus ligands. In a previous study, it was found that (p-cymene)RuI2(P{OCH2}3CEt) (1) could be rapidly and cleanly phenylated with commercially available phenylmagnesium bromide to yield (p-cymene)RuI(Ph)(P{OCH2}3CEt) in good yield. To test the scope of this reaction, complexes 2-4 were phenylated under similar conditions as that of 1, which showed complete conversion to their respective (p-cymene)RuI(Ph)PR3 complex (PMe3 = 5, P(OMe3) = 6 and PPh3 = 7). Compounds 2-7 were characterized 1H, 13C, and 31P NMR spectroscopy and complexes 2, 5, and 6 were also characterized by single crystal X-ray diffraction studies. In addition, the stabilities of 5-7 were examined, which revealed complex 5 and 6 are highly sensitive to air and moisture, while 7 is quite stable for days when stored in air. Presented herein is the synthesis, characterization, and reactivity of these complexes.
