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Full-Text Articles in Physical Sciences and Mathematics
Proton-Coupled Reduction Of An Iron Nitrosyl Porphyrin In The Protic Ionic Liquid Nanodomain, Abderrahman Atifi, Piotr J. Mak, Michael D. Ryan
Proton-Coupled Reduction Of An Iron Nitrosyl Porphyrin In The Protic Ionic Liquid Nanodomain, Abderrahman Atifi, Piotr J. Mak, Michael D. Ryan
Chemistry Faculty Research and Publications
The one-electron reduction of many molecules becomes much more favorable if combined with proton transfers or strong hydrogen bonding. Protic room temperature ionic liquids (RTILs), which can form nanodomains in solutions with molecular solvents (MS), can provide an efficient avenue for this process. In this work, we report on the voltammetry, UV/visible and resonance Raman spectroelectrochemistryof Fe(TPP)(NO) in the presence of aprotic/protic ammonium-based ionic liquids. While aprotic RTILs did shift the reduction to more positive potentials, similar shifts could be observed at much lower concentrations of diethylmethylammonium triflate (HAmOTf, a protic ionic liquid). Deconvolution of the rotating ring-disk electrode (RRDE) …
Investigation Of Solvation And Solvent Coordination Effects In Iron Porphyrin Nitrosyls By Infrared Spectroelectrochemistry And Dft Calculations, Md. Hafizur Rahman, Michael D. Ryan
Investigation Of Solvation And Solvent Coordination Effects In Iron Porphyrin Nitrosyls By Infrared Spectroelectrochemistry And Dft Calculations, Md. Hafizur Rahman, Michael D. Ryan
Chemistry Faculty Research and Publications
Visible and infrared spectroelectrochemistry of Fe(OEPone)(NO) (H2OEPone = octaethylporphinone) were examined in methylene chloride and THF. The visible spectra of Fe(OEPone)(NO) were similar in both solvents. Unlike other ferrous porphyrin nitrosyls, a six-coordinate complex was formed with THF as a ligand. This led to two nitrosyl bands in the infrared spectrum. The absorbance of these bands depended on the concentration of THF in the solution. Solvation and coordination effects on the carbonyl and nitrosyl bands were observed for both the nitrosyl and reduced-nitrosyl complexes. DFT calculations were carried out to interpret the spectral changes.