Mieres-Perez Joel, Lucht Karsten, Trosien Iris, Sander Wolfram, Sanchez-Garcia Elsa, Morgenstern Karina
Universität Duisburg-Essen, Computational Biochemistry, Universitätsstr.2, D-45141 Essen, Germany.
Ruhr-Universität Bochum, Lehrstuhl für Physikalische Chemie I, Universitätsstr.150, D-44801 Bochum, Germany.
J Am Chem Soc. 2021 Mar 31;143(12):4653-4660. doi: 10.1021/jacs.0c12995. Epub 2021 Feb 18.
Metal carbenes are key intermediates in a plethora of homogeneous and heterogeneous catalytic processes. However, despite their importance to heterogeneous catalysis, the influence of surface attachment on carbene reactivity has not yet been explored. Here, we reveal the interactions of fluorenylidene (FY), an archetypical aromatic carbene of extreme reactivity, with a Ag(111) surface. For the first time, the interaction of a highly reactive carbene with a metal surface could be studied by scanning tunneling microscopy (STM). FY chemisorbs on Ag(111) with an estimated desorption energy of 3 eV, forming a surface bound silver-carbene complex. The surface interaction leads to a switching of the electronic ground state of FY from triplet to singlet, and to controlled chemical reactivity. This atomistic understanding of the interplay between carbenes and metal surfaces opens the way for the development of novel classes of catalytic systems based on surface metal carbenes.
金属卡宾是众多均相和多相催化过程中的关键中间体。然而，尽管它们对多相催化很重要，但表面附着对卡宾反应性的影响尚未得到探索。在这里，我们揭示了芴叉（FY），一种具有极高反应活性的典型芳香族卡宾，与Ag(111)表面的相互作用。首次能够通过扫描隧道显微镜（STM）研究高反应活性卡宾与金属表面的相互作用。FY以估计为3 eV的脱附能量化学吸附在Ag(111)上，形成表面结合的银 - 卡宾络合物。表面相互作用导致FY的电子基态从三重态转变为单重态，并产生可控的化学反应性。这种对卡宾与金属表面相互作用的原子层面理解为基于表面金属卡宾的新型催化体系的开发开辟了道路。
