Herburger Andreas, Ončák Milan, Barwa Erik, van der Linde Christian, Beyer Martin K
Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstraße 25, 6020 Innsbruck, Austria.
Int J Mass Spectrom. 2019 Jan;435:101-106. doi: 10.1016/j.ijms.2018.10.019. Epub 2018 Oct 12.
Electrochemical activation of carbon dioxide in aqueous solution is a promising way to use carbon dioxide as a C1 building block. Mechanistic studies in the gas phase play an important role to understand the inherent chemical reactivity of the carbon dioxide radical anion. Here, the reactivity of CO (HO) with 3-butyn-1-ol is investigated by Fourier transform ion cyclotron (FT-ICR) mass spectrometry and quantum chemical calculations. Carbon-carbon bond formation takes places, but is associated with a barrier. Therefore, bond formation may require uptake of several butynol molecules. The water molecules slowly evaporate from the cluster due to the absorption of room temperature black-body radiation. When all water molecules are lost, butynol evaporation sets in. In this late stage of the reaction, side reactions occur including H atom transfer and elimination of HOCO.
水溶液中二氧化碳的电化学活化是将二氧化碳用作C1结构单元的一种很有前景的方法。气相中的机理研究对于理解二氧化碳自由基阴离子的固有化学反应性起着重要作用。在此，通过傅里叶变换离子回旋共振（FT-ICR）质谱和量子化学计算研究了CO₂⁻(H₂O)与3-丁炔-1-醇的反应活性。碳-碳键形成，但与一个势垒相关。因此，键的形成可能需要吸收几个丁炔醇分子。由于吸收室温黑体辐射，水分子从团簇中缓慢蒸发。当所有水分子都失去时，丁炔醇蒸发开始。在反应的这个后期阶段，会发生包括氢原子转移和HOCO消除在内的副反应。
