Towards a Conceptual Transfer of Gas-Phase Ion-Chemistry into the Condensed Phase

该研究项目的目的是将气相离子化学的概念转变为凝聚相。由于这两种环境的条件截然不同，这种转移不是微不足道的，到目前为止还没有得到充分的研究。相反，质谱学方法越来越多地被用于研究溶液中的过程。因此，深入了解这两个阶段化学反应的关系是至关重要的。从这些努力中得出的一个目标是将在气相实验中获得的结果用于实际。重点放在小分子的活化、成键反应和氧原子转移上。最终目标是开发气相激发的催化转化。为了实现这一目标，我们使用模型系统，我们在气相实验和溶液中都研究了模型系统的反应性。这些实验能够确定溶剂分子、反离子和额外的连接对本征反应模式的影响。其中一个目标模型系统涉及异双金属硬币-金属铂-络合物。在气相实验中，裸双原子阳离子参与了甲烷和氨的脱氢C-N键偶联反应。另一个方向是研究配体交换过程。在第二个资助期，重点是金属-氧络合物的研究。这一方向的灵感来自双原子过渡金属氧阳离子丰富的气相化学。在我们的气相模拟方法的框架内，我们希望产生适当的协调体系，包括质谱学和溶液中的体系。我们将研究这些系统的反应性作为协调环境的函数。

The aim of the research project is the conceptual transfer of gas-phase ion-chemistry into the condensed phase. Due to the very different conditions in both environments, such a transfer is not trivial and has not been studied sufficiently so far. Conversely, mass-spectrometric methods are increasingly used to study processes in solution. Therefore, it is crucial to gain a deeper understanding of the relationship of chemical reactivity in both phases. A goal derived from these efforts is to make practical use of the results gained in gas-phase experiments. The focus is on the activation of small molecules, bond-forming reactions, and oxygen-atom transfer. The ultimate goal is the development of gas phase-inspired catalytic transformations. Towards this goal, we use model systems, the reactivity of which we investigate both in gas-phase experiments and in solution. These experiments enable the determination of the influence of solvent molecules, counterions, and additional ligation on intrinsic-reactivity patterns. One of the targeted model systems involves heterobimetallic coinage-metal platinum-complexes. The bare diatomic cations mediate dehydrogenative C–N-bond coupling of methane and ammonia in gas-phase experiments. Another direction constitutes the investigation of ligand-exchange processes. In the second funding period, the focus is on investigations of metal-oxo complexes. This direction is inspired by the rich gas-phase chemistry of diatomic transition-metal oxo cations. In the framework of our gas-phase mimetic approach, we want to generate appropriately coordinated systems both mass-spectrometrically and in solution. We will study the reactivity of these systems as a function of the coordination environment.