Quantum Tunneling-Mediated Interfacial Synthesis of a Benzofuran Derivative.
Quantum Tunneling-Mediated Interfacial Synthesis of a Benzofuran Derivative.
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DOI：
10.1002/anie.201904030
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发表时间：
2019-07
影响因子：
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通讯作者：
T. Paintner;Jonas Björk;P. Du;S. Klyatskaya;M. Paszkiewicz;Raphael Hellwig;Martin Uphoff;M. A. Öner;Edoardo Cuniberto;P. S. Deimel;Yi‐Qi Zhang;Carlos‐Andres Palma;F. Allegretti;M. Ruben;J. Barth;F. Klappenberger
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文献类型：
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作者：
T. Paintner;Jonas Björk;P. Du;S. Klyatskaya;M. Paszkiewicz;Raphael Hellwig;Martin Uphoff;M. A. Öner;Edoardo Cuniberto;P. S. Deimel;Yi‐Qi Zhang;Carlos‐Andres Palma;F. Allegretti;M. Ruben;J. Barth;F. Klappenberger
涉及质子量子隧穿的反应途径是化学和生物学的基础。它们负责星际合成、化合物的降解和异构化、扩散过程、酶活性和蛋白质动力学的基本方面。表面条件被证明可以打开有机合成的替代途径，通常是在溶液中无法到达的复杂途径。在这里，我们利用扫描隧道显微镜、x射线电子能谱和密度泛函理论研究了吸附在Ag（111）表面的分子物种的氢烷氧基化反应。呋喃环闭合在低温（低至150 K）下进行，没有可检测到的副反应。我们从理论上揭示了质子隧穿介导的途径，并通过氘化衍生物的动力学同位素效应证实了它的主要贡献。我们的发现为复杂的界面化学转化提供了无与伦比的见解，并为基于量子隧道的表面合成开辟了未知的途径。
Reaction pathways involving quantum tunneling of protons are fundamental to chemistry and biology. They are responsible for essential aspects of interstellar synthesis, the degradation and isomerization of compounds, diffusion processes, enzymatic activity, and protein dynamics. On-surface conditions were demonstrated to open alternative routes for organic synthesis often with intricate pathways not accessible in solution. Here, we investigate a hydroalkoxylation reaction of a molecular species adsorbed on the Ag(111) surface with scanning tunneling microscopy complemented by X-ray electron spectroscopies and density functional theory. The furan ring-closure proceeds at low temperature (down to 150 K) and without detectable side-reactions. We theoretically unravel a proton-tunneling-mediated pathway and experimentally confirm its dominant contribution by the kinetic isotope effect with a deuterated derivative. Our findings provide unmatched insight into complex interfacial chemical transformations and open unexplored routes for on-surface synthesis based in quantum tunneling.