Chemistry of Transient Species in Water Clusters

水溶液中的电子诱导反应直接或间接地促成了许多化学过程，从有机合成到金属电极上的光化学分解水到金属结构的腐蚀。这些反应的短暂中间体可以在水团簇中稳定下来。在质谱仪中，带电中间体被溶剂化的水团簇与中性反应伙伴的碰撞中，可以研究单个反应步骤。从水合电子与氯化氢气体的反应可望对水溶液中的电子诱导键断裂有基本的了解。生物分子中的电子诱导键断裂与生命科学有关。磷酸三乙酯作为DNA骨架的模型体系，其在水溶液中对电子诱导反应的稳定性有待计划的实验。以一系列含三至六元环的饱和环烃为例，研究了环应变对有机分子电子诱导开环的影响。电子也可以由活性金属中心提供，如单价过渡金属离子。有了这些系统，各种类型的反应将被研究。卤代烃与水合电子碰撞时，卤素-碳键发生断裂。通过与水合过渡金属离子的反应，揭示了金属卤化物的沉淀对反应路径的影响。通过电子转移还原有机分子是乙腈与单价水合过渡金属离子反应的另一个例子。硫磺分子如甲硫醇或二甲基二硫醚，除了电子诱导的键断裂外，还能形成金属硫键。对这些反应的研究增加了实验的复杂性。

Electron induced reactions in aqueous solution contribute directly and indirectly to a multitude of chemical processes, ranging from organic synthesis via photochemical water splitting on metal electrodes to corrosion of metallic structures. Short lived intermediates of these reactions can be stabilized in water clusters. Individual reaction steps can be studied in the collision of a water cluster, in which the charged intermediate is solvated, with a neutral reaction partner in a mass spectrometer. Fundamental insight into electron induced bond cleavage in aqueous solution is expected from the reactions of hydrated electrons with gaseous hydrogen chloride. Electron induced bond cleavage in biomolecules is relevant for life sciences. Triethyl phosphate serves as a model system for the DNA backbone, its stability against electron induced reactions in aqueous solution is subject to a planned experiment. The influence of ring strain on the theoretically predicted electron induced ring opening of organic molecules is investigated with a series of saturated cyclic hydrocarbons, featuring three- to six-membered rings. Electrons may also be provided by a reactive metal center, like a monovalent transition metal ion. With these systems, various types of reactions are going to be investigated. Halogenated hydrocarbons undergo cleavage of the halogen-carbon bond upon collision with a hydrated electron. The corresponding reactions with hydrated transition metal ions are supposed to reveal the influence of the precipitation of the metal halogenide on the reaction path. Reduction of organic molecules by electron transfer is another example which will be studied in the reaction of acetonitrile with monovalent hydrated transition metal ions. Sulfur containing molecules like methyl mercaptane or dimethyl disulfide are able to form metal-sulfur bonds in addition to electron induced bond cleavage. The investigation of these reactions adds an additional degree of complexity to the experiments.