Graduation Semester and Year
2020
Language
English
Document Type
Dissertation
Degree Name
Doctor of Philosophy in Chemistry
Department
Chemistry and Biochemistry
First Advisor
Rasika Dias
Abstract
Trinuclear copper pyrazolate complexes (copper trimers) function as excellent precursors to synthesize multinuclear complexes of copper. Using highly fluorinated pyrazolates as supporting ligands, we have successfully synthesized and isolated several unique complexes of copper with alkene (e.g., ethylene), alkynes (e.g., 3-hexyne, butyne, acetylene, etc.) and carbon monoxide from the copper trimers. Synthetic details, solid-state structures, and physico-chemical properties of a series of multinuclear complexes have been studied. Chapter 2 of this research work focuses on the olefin/paraffin separation technology. For this we have succesfully synthesized a novel, highly fluorinated copper pyrazolate complex, that undergoes remarkable structural rearrangement forming a dinuclear species, [(3,4,5-(CF3)3Pz)Cu(H2C=CH2)]2, when exposed to ethylene. We have discussed in detail the benefit of this transformation, and how it can be efficiently used for separation of olefins from a mixture of gases. Chapter 3 covers the synthesis, study of photophysical properties and computational analysis of di- and tetranuclear complexes of copper with internal alkynes. This class of molecules show interesting photoluminescence at different temperatures, and in different solvents. Copper trimer also acts as a powerful catalyst for alkyne transformations as evident from its ability to catalyze the alkyne C(sp)–H bond for carboxylation with CO2, azide-alkyne cycloaddition and hydrothiolation. The reaction intermediates for these catalytic reactions were isolated and investigated in chapter 3. Chapter 4 describes the carbonyl chemistry of multinuclear copper pyrazolates and the effects of additional donors such as chloride, bromide, and [3,5-(CF3)2Pz]− ions on the stability of the resulting copper(I) carbonyl adducts. Accordingly, {[3,5-(CF3)2Pz]Cu(CO)}2, {[4-Cl-3,5-(CF3)2Pz]Cu(CO)}2, {[3,4,5-(CF3)3Pz]Cu(CO)}2, [NEt4][{[3,5-(CF3)2Pz]Cu(CO)}4(μ4-Br)], [NEt4]{[3,5-(CF3)2Pz]3Cu2(CO)2}, [NEt4][{[4-Cl-3,5-(CF3)2Pz]Cu(CO)}4(μ4-Br)], [NEt4][{[4-Cl-3,5-(CF3)2Pz]Cu(CO)}4(μ4-Cl)] and [{[4-Cl-3,5-(CF3)2Pz]Cu(CO)}2(μ2-CH3CN)] were synthesized and characterized. Theoretical calculations were also performed to study the bonding energy of the synthesized complexes.
Keywords
Coordination Chemistry, Ligands, Pyrazole, Copper, Copper-pyrazolates, Synthesis, Olefin/Paraffin separation, Ethylene, Acetylene, Alkynes, Carbon monoxide, Catalysis, Luminescence, Structure and Bonding, Chemisorption, Adsorption Isotherms, Enthalpy, Variable Temperature NMR
Disciplines
Chemistry | Physical Sciences and Mathematics
License
This work is licensed under a Creative Commons Attribution-NonCommercial-Share Alike 4.0 International License.
Recommended Citation
Parasar, Devaborniny, "SYNTHESIS, STUDY, AND APPLICATIONS OF HIGHLY FLUORINATED COPPER PYRAZOLATE COMPLEXES OF SMALL ALKENE, ALKYNES AND CARBON MONOXIDE" (2020). Chemistry & Biochemistry Dissertations. 246.
https://mavmatrix.uta.edu/chemistry_dissertations/246
Comments
Degree granted by The University of Texas at Arlington