Isolating the Effects of the Proton Tunneling Distance on Proton-Coupled Electron Transfer in a Series of Homologous Tyrosine-Base Model Compounds
| Autor: | Sascha Ott, Starla D. Glover, Todd F. Markle, Leif Hammarström, Giovanny A. Parada |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
chemistry.chemical_classification
Range (particle radiation) Proton Base (chemistry) 010405 organic chemistry Quinoline General Chemistry 010402 general chemistry Photochemistry 01 natural sciences Biochemistry Catalysis 0104 chemical sciences Electron transfer chemistry.chemical_compound Crystallography Colloid and Surface Chemistry chemistry Covalent bond Proton-coupled electron transfer Spectroscopy |
| Zdroj: | Journal of the American Chemical Society. 139:2090-2101 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.6b12531 |
| Popis: | The distance dependence of concerted proton-coupled electron transfer (PCET) reactions was probed in a series of three new compounds, where a phenol is covalently bridged by a 5, 6, or 7 membered carbocycle to the quinoline. The carbocycle bridge enforces the change in distance between the phenol oxygen (proton donor) and quinoline nitrogen (proton acceptor), dO···N, giving rise to values ranging from 2.567 to 2.8487 A, and resulting in calculated proton tunneling distances, r0, that span 0.719 to 1.244 A. Not only does this series significantly extend the range of distances that has been previously accessible for experimental distance dependent PCET studies of synthetic model compounds, but it also greatly improves the isolation of dO···N as a variable compared to earlier reports. Rates of PCET were determined by time-resolved optical spectroscopy with flash-quench generated [Ru(bpy)3]3+ and [Ru(dce)3]3+, where bpy = 2,2′-bipyridyl and dce = 4,4′-dicarboxyethylester-2,2′-bipyridyl. The rates increased as... |
| Databáze: | OpenAIRE |
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