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Direct Evidence for the Origin of Bis-Gold Intermediates: Probing Gold Catalysis with Mass Spectrometry

机译:双金中间体的起源的直接证据:用质谱探测金催化

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摘要

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.
机译:利用原位反应质谱技术研究了金催化炔烃的水合反应。通过监测溶液在不同条件下的反应过程(常规和非常稀释的催化剂浓度,不同的pH值),并检查早期反应阶段(混合后1-2毫秒)中与MS发生的反应,我们收集了一系列实验证据支持双金复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-双金配合物不是亲核加成的活性中间体。取而代之的是,形成双还原的复合物> C 对于此催化过程至关重要。

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