Chen Qiang, Zhao Yan-Xia, Jiang Li-Xue, Chen Jiao-Jiao, He Sheng-Gui
State Key Laboratory for Structural Chemistry of, Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center of Excellence in Molecular Sciences, Beijing, 100190, P. R. China.
Angew Chem Int Ed Engl. 2018 Oct 22;57(43):14134-14138. doi: 10.1002/anie.201808780. Epub 2018 Oct 1.
The use of CH and CO to produce value-added chemicals via direct C-C coupling is a challenging chemistry problem because of the inertness of these two molecules. Herein, mass spectrometric experiments and high-level quantum-chemical calculations have identified the first diatomic species (CuB ) that can couple CH with CO under thermal collision conditions to produce ketene (H C=C=O), an important intermediate in synthetic chemistry. The order to feed the reactants (CH and CO ) is important and CH should be firstly fed to produce the C product. Molecular-level mechanisms including control of product selectivity have been revealed for coupling of CH with CO under mild conditions.
由于CH和CO这两种分子的惰性，通过直接碳-碳偶联来生产增值化学品是一个具有挑战性的化学问题。在此，质谱实验和高水平量子化学计算确定了首个双原子物种（CuB），它能够在热碰撞条件下使CH与CO偶联生成乙烯酮（H₂C=C=O），这是合成化学中的一种重要中间体。反应物（CH和CO）的进料顺序很重要，应首先进料CH以生成含碳产物。已经揭示了在温和条件下CH与CO偶联的分子水平机制，包括产物选择性的控制。
