Synthetic oxo-bridged manganese(porphyrin)-copper complexes derived from dioxygen chemistry
- UNCG Author/Contributor (non-UNCG co-authors, if there are any, appear on document)
- Dahlia S. Porter-Cole (Creator)
- Institution
- The University of North Carolina at Greensboro (UNCG )
- Web Site: http://library.uncg.edu/
- Advisor
- Shabnam Hematian
Abstract: This report investigates the expanded library of manganese/copper oxo-bridged complexes derived from dioxygen chemistry. Our group previously reported a Mn/Cu system, [(tmpa)CuII-O-MnIII(TPP)]+, formed from O2 chemistry at ambient conditions, where [(TPP) MnII] in the presence of a copper(I) complex showed unprecedented reactivity toward dioxygen. The reaction proceeds through a series of manganese/copper/O2 adducts forming a final oxo-bridged complex. This report introduces derivatized copper chelates such as the electron poor ligand, F2TMPA, and electron rich ligand, MeTFE-TMPA. This report also aims to investigate how the coordination environment of the copper chelates influences the µ-oxo manganese/copper complexes. This is accomplished by including tridentate copper chelates such as AN and MePY2. Changes to the porphyrin, (Por), include the addition of electron poor groups in F8TPPH2 as compared to the parent system, TPPH2. UV-vis, 1HNMR, 19FNMR, and Infrared spectroscopies were used to characterize the oxo-bridged assemblies. Analysis of UV-vis spectra has shown that variation of the copper chelates, and porphyrin rings has a profound effect on the absorption intensities of the LMCT and Soret bands. 1HNMR and 19FNMR results indicate an established connection through an oxo-bridge in the new [(L)CuII-O-MnIII(Por)]+ series by tracking the proton and fluorine chemical shifts as a result of functionalization. This is accomplished by comparing the 1HNMR and 19FNMR of analogues of the anticipated reactants, [(Por)MnII] and [(L)CuI][B(C6F5)4]2, monomeric oxidized complexes, [(Por)MnIIICl], [(Por)MnIIITHF]SbF6, [(L)CuII][B(C6F5)4]2, and the oxo-bridged products, [(L)CuII-O-MnIII(Por)]+. Infrared spectroscopy is also used to examine and compare the monomeric complexes, to the vibrational features of the newly formed oxo-bridged species. [This abstract may have been edited to remove characters that will not display in this system. Please see the PDF for the full abstract.]
Synthetic oxo-bridged manganese(porphyrin)-copper complexes derived from dioxygen chemistry
PDF (Portable Document Format)
5350 KB
Created on 8/1/2024
Views: 25
Additional Information
- Publication
- Thesis
- Language: English
- Date: 2024
- Subjects
- Dioxygen activation
- Metal complexes
- Porphyrins
- Chelates