Directing isomerization reactions of cumulenes with electric fields
| Autor: | Qi Zou, Michael L. Steigerwald, Fay Ng, Colin Nuckolls, Yaping Zang, Brandon Fowler, Latha Venkataraman, Jingjing Yang, Tianren Fu, Hexing Li |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Materials science
Field (physics) Science Molecular electronics General Physics and Astronomy Ionic bonding 02 engineering and technology 010402 general chemistry 7. Clean energy 01 natural sciences Chemical reaction General Biochemistry Genetics and Molecular Biology Article Catalysis chemistry.chemical_compound Electric field lcsh:Science Multidisciplinary Cumulene General Chemistry 021001 nanoscience & nanotechnology Transition state 0104 chemical sciences chemistry Chemical physics lcsh:Q 0210 nano-technology Electrocatalysis Isomerization |
| Zdroj: | Nature Communications, Vol 10, Iss 1, Pp 1-7 (2019) Nature Communications |
| ISSN: | 2041-1723 |
| DOI: | 10.1038/s41467-019-12487-w |
| Popis: | Electric fields have been proposed as having a distinct ability to catalyze chemical reactions through the stabilization of polar or ionic intermediate transition states. Although field-assisted catalysis is being researched, the ability to catalyze reactions in solution using electric fields remains elusive and the understanding of mechanisms of such catalysis is sparse. Here we show that an electric field can catalyze the cis-to-trans isomerization of [3]cumulene derivatives in solution, in a scanning tunneling microscope. We further show that the external electric field can alter the thermodynamics inhibiting the trans-to-cis reverse reaction, endowing the selectivity toward trans isomer. Using density functional theory-based calculations, we find that the applied electric field promotes a zwitterionic resonance form, which ensures a lower energy transition state for the isomerization reaction. The field also stabilizes the trans form, relative to the cis, dictating the cis/trans thermodynamics, driving the equilibrium product exclusively toward the trans. Electric fields have been proposed as having a distinct ability to catalyse chemical reactions through stabilizing polar intermediates. Here, the authors show that electric fields can catalyse the cis-to-trans isomerization reactions of cumulenes in solution in a scanning tunnelling microscope |
| Databáze: | OpenAIRE |
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