Lu Mei, Su Yijin, Zhao Pengyi, Ye Xiaohan, Cai Yi, Shi Xiaodong, Masson Eric, Li Fengyao, Campbell J Larry, Chen Hao
Center for Intelligent Chemical Instrumentation, Department of Chemistry and Biochemistry & Edison Institute of Biology, Ohio University, Athens, OH, 45701, USA.
Department of Chemistry, University of South Florida, Tampa, FL, 33620, USA.
Chemistry. 2018 Feb 9;24(9):2144-2150. doi: 10.1002/chem.201703666. Epub 2018 Jan 17.
Gold-catalyzed alkyne hydration was studied by using in situ reacting mass spectrometry (MS) technology. By monitoring the reaction process in solution under different conditions (regular and very diluted catalyst concentrations, different pH values) and examining the reaction occurrence in the early reaction stage (1-2 ms after mixing) with MS, we collected a series of experimental evidence to support that the bis-gold complex is a potential key reaction intermediate. Furthermore, both experimental and computational studies confirmed that the σ,π-bis-gold complexes are not active intermediates toward nucleophilic addition. Instead, formation of geminally diaurated complex C is crucial for this catalytic process.
采用原位反应质谱（MS）技术研究了金催化的炔烃水合反应。通过监测不同条件下（常规和极稀催化剂浓度、不同pH值）溶液中的反应过程，并利用质谱检测反应早期阶段（混合后1-2毫秒）的反应发生情况，我们收集了一系列实验证据来支持双金配合物是潜在的关键反应中间体。此外，实验和计算研究均证实，σ,π-双金配合物对亲核加成反应不是活性中间体。相反，偕二金配合物C的形成对该催化过程至关重要。
