Brinkmann Nils, Austin Dave, Ashraf Bushra, Le Duy, Rahman Talat S, Al-Shamery Katharina
Institute of Chemistry, Carl von Ossietzky University of Oldenburg, Carl-von-Ossietzky-Straße 9-11, 26129 Oldenburg, Germany.
Department of Physics, University of Central Florida, Orlando, Florida 32816, United States.
J Am Chem Soc. 2025 May 21;147(20):16964-16971. doi: 10.1021/jacs.5c00567. Epub 2025 May 12.
This study investigates the roles of ethylene and ethylidyne in the surface chemistry of -methylaniline (NMA) on Pt(111). Using X-ray photoelectron spectroscopy, temperature-programmed desorption, and density functional theory calculations, we demonstrate that ethylidyne is not merely a passive spectator species but actively contributes to hydroamination. It facilitates C-N bond formation by transferring a methyl group to NMA, leading to the formation of ,-dimethylaniline. Additionally, it stabilizes reaction intermediates and suppresses the decomposition of NMA. This works demonstrates, in contrast to the widely accepted notion, that ethylidyne is not just an inert spectator species; rather, it plays a dual role as both an active reaction partner and a stabilizer. In addition, the coadsorption of ethylene on an NMA-precovered surface shows a side reaction of ethylene with the decomposition products of NMA.
本研究调查了乙烯和次乙基在对甲基苯胺（NMA）于Pt(111)表面化学过程中的作用。通过X射线光电子能谱、程序升温脱附以及密度泛函理论计算，我们证明次乙基并非仅仅是一个被动的旁观物种，而是对氢胺化反应有积极贡献。它通过将一个甲基转移至NMA促进C-N键的形成，从而导致α,β-二甲基苯胺的生成。此外，它稳定反应中间体并抑制NMA的分解。与广泛接受的观念相反，本研究表明次乙基并非仅仅是一个惰性的旁观物种；相反，它兼具活性反应伙伴和稳定剂的双重作用。此外，乙烯在预先覆盖NMA的表面上的共吸附显示出乙烯与NMA分解产物的副反应。
